Reaction of carbon black with diazonium salts, resultant carbon black products and their uses

ABSTRACT

Processes for preparing a carbon black product having an organic group attached to the carbon black. In one process at least one diazonium salt reacts with a carbon black in the absence of an externally applied electric current sufficient to reduce the diazonium salt. In another process at least one diazonium salt reacts with a carbon black in a protic reaction medium. Carbon black products which may be prepared according to process of the invention are described as well as uses of such carbon black products in plastic compositions, rubber compositions, paper compositions, and textile compositions.

[0001] This application is a continuation of U.S. patent applicationSer. No. 09/257,237 filed Feb. 25, 1999, which is a continuation of U.S.patent application Ser. No. 09/105,007, filed Jun. 26, 1998, which is acontinuation of prior U.S. patent application Ser. No. 08/572,525, filedDec. 14, 1995, which is a continuation-in-part of U.S. patentapplication Ser. No. 08/356,660, filed Dec. 15, 1994, now abandoned, andare incorporated in their entirety by reference herein.

FIELD OF THE INVENTION

[0002] This invention relates to a process for the preparation of carbonblack products. The process involves reacting a diazonium salt with acarbon black to yield a carbon black product having an organic groupattached to the carbon black. The invention also relates to new carbonblack products and their uses.

BACKGROUND OF THE INVENTION

[0003] Much effort has been expended over the last several decades tomodify the surface chemistry of carbon black. While it is possible todeposit physically adsorbed material onto the surface of carbon black,permanently changing the surface chemistry of carbon black issubstantially more difficult.

[0004] Some processes for chemically changing the surface of carbonblack are known and used commercially. For example, it is well knownthat a carbon black surface can be oxidized with a variety of treatingagents. Surface oxidation is used to make some commercial products.Sulfonation using sulfuric acid or chlorosulfuric acid and halogenationof a carbon black surface are also known. Some known methods forgrafting polymers to the carbon black surface are reviewed by Tsubakowain Polym. Sci., Vol. 17, pp 417-470, 1992. Se also U.S. Pat. No.4,014,844 which grafts polymers onto carbon black by contacting thecarbon black with the polymer and heating.

[0005] U.S. Pat. No. 3,479,300 describes carbon catalyst compositionsand a process for their production. The catalyst compositions areprepared by treating carbon particles with an alkali or alkaline earthmetal and subsequently treating the resulting carbon/metal compositionwith a solvating ether. The carbon portions of the catalyticcompositions can be reacted with various reagents, including organiccompounds, to produce carbon compositions.

[0006] U.S. Pat. No. 3,043,708 describes modified carbon blacks havinghydrocarbon groups chemically attached to the surface of the carbonblack. The modified carbon blacks are prepared by reacting carbon blackwith an alkylating agent in the presence of a Friedel-Crafts typereaction catalyst. The hydrocarbon groups which reportedly can attach tothe surface of the carbon black include aliphatic and aromatic groups. Amodified carbon black containing aryl groups attached to the surface ofa carbon black is reported as being preparable by reacting a halogenatedcarbon black with an aromatic hydrocarbon in the presence of aFriedel-Crafts type catalyst. U.S. Pat. No. 3,025,259 describes rubbercompositions containing the modified carbon blacks of U.S. Pat. No.3,043,708.

[0007] U.S. Pat. No. 3,335,020 describes modified carbon blacks wherethe carbon black is treated with benzene which is then polymerized onthe carbon black. To prepare these modified carbon blacks, benzene andcarbon black are mixed with a Lewis Acid catalyst under anhydrousconditions for about ten minutes. The benzene on the carbon black isthen polymerized to parapolyphenyl by means of a combinationco-catalyst-oxidizing agent and is reportedly thereby bonded to thecarbon black.

[0008] U.S. Pat. Nos. 2,502,254 and 2,514,236 describe the manufactureof pigments containing carbon black. U.S. Pat. No. 2,502,254 reportsthat highly dispersed pigments suitable for mass pigmentation of viscosecan be obtained by generating an azo pigment in the presence of carbonblack.

[0009] The pigment is produced by coupling a diazotized amine andanother usual intermediate for a yellow, orange, or red pigment in thepresence of carbon black in one or the other of the aqueous solutions ofwhich the mixing brings about the coupling. U.S. Pat. No. 2,514,236reports that this process can also prepare a chocolate brown pigment bycoupling one molecular proportion of a tetrazotized benzidine with twomolecular proportions of an arylmethylpyrazolone in the presence ofcarbon black.

[0010] PCT Patent Application No. WO 92/13983 describes a process formodifying the surfaces of carbon-containing materials by electrochemicalreduction of diazonium salts. The process is reportedly applicable, inparticular, to carbon plates and carbon fibers for composite materials.Carbon-containing materials modified by the process are also described.Electrochemical reduction of diazonium salts containing functionalizedaryl radicals to covalently modify carbon surfaces is also described inDelmar et al., J Am. Chem. Soc. 1992, 114, 5883-5884.

[0011] According to WO 92/13983, the process for modifying the surfaceof a carbon-containing material consists of grafting an aromatic groupto the surface of this material by electrochemical reduction of adiazonium salt including this aromatic group. The carbon-containingmaterial is placed in contact with a diazonium salt solution in anaprotic solvent and is negatively charged with respect to an anode whichis also in contact with the diazonium salt solution. Use of a proticsolvent is reported to prevent the electrochemical process fromproducing the intended product as a result of reducing the diazoniumtriple bond to yield a hydrazine.

[0012] Despite the technology discussed above, there remains a need tomodify the surface chemistry of carbon black and impart desiredproperties to the carbon black.

SUMMARY OF THE INVENTION

[0013] Accordingly, the present invention relates to processes forpreparing a carbon black product having an organic group attached to thecarbon black. One process comprises the step of reacting at least onediazonium salt with a carbon black in the absence of an externallyapplied electric current sufficient to reduce the diazonium salt.Another process comprises the step of reacting at least one diazoniumsalt with a carbon black in a protic reaction medium.

[0014] Other embodiments of the invention relate to novel carbon blackproducts, which may be prepared according to a process of the invention.The carbon black products may be used in the same applications asconventional carbon blacks. Such uses include, but are not limited to,plastic compositions, aqueous inks, aqueous coatings, rubbercompositions, paper compositions, and textile compositions.

[0015] The description which follows sets out additional features andadvantages of the invention. These functions will be apparent from thatdescription or may be learned by practice of the invention as described.The objectives and other advantages will be realized and attained by theprocesses, products, and compositions particularly pointed out in thedescription below and the appended claims.

DETAILED DESCRIPTION

[0016] Processes for Preparing a Carbon Black Product

[0017] A first embodiment of the invention provides processes forpreparing a carbon black product having an organic group attached to thecarbon black. One process involves the reaction of at least onediazonium salt with a carbon black in the absence of an externallyapplied current sufficient to reduce the diazonium salt. That is, thereaction between the diazonium salt and the carbon black proceedswithout an external source of electrons sufficient to reduce thediazonium salt. Mixtures of different diazonium salts may be used in theprocess of the invention. This process can be carried out under avariety of reaction conditions and in any type of reaction medium,including both protic and aprotic solvent systems or slurries.

[0018] In another process, at least one diazonium salt reacts with acarbon black in a protic reaction medium. Mixtures of differentdiazonium salts may be used in this process of the invention. Thisprocess can also be carried out under a variety of reaction conditions.

[0019] Preferably, in both processes, the diazonium salt is formed insitu. If desired, in either process, the carbon black product can beisolated and dried by means known in the art. Furthermore, the resultantcarbon black product can be treated to remove impurities by knowntechniques. The various preferred embodiments of these processes arediscussed below and are shown in the examples.

[0020] Any carbon black may be used in the processes of this invention.The resulting carbon black products are useful in applications known forconventional carbon blacks. The properties of the carbon blacks areselected based upon the intended application. More importantly, theprocesses of this invention can be used to provide carbon black productshaving advantageous properties not associated with conventional carbonblacks.

[0021] The processes of the invention can be carried out under a widevariety of conditions and in general are not limited by any particularcondition. The reaction conditions must be such that the particulardiazonium salt is sufficiently stable to allow it to react with thecarbon black. Thus, the processes can be carried out under reactionconditions where the diazonium salt is short lived. As the examplesbelow illustrate, the reaction between the diazonium salt and the carbonblack occurs, for example, over a wide range of pH and temperature. Theprocesses can be carried out at acidic, neutral, and basic pH.Preferably, the pH ranges from about 1 to 9. The reaction temperaturemay preferably range from 0° C. to 100° C.

[0022] Diazonium salts, as known in the art, may be formed for exampleby the reaction of primary amines with aqueous solutions of nitrousacid. A general discussion of diazonium salts and methods for theirpreparation is found in Morrison and Boyd, Organic Chemistry, 5th Ed.,pp. 973-983, (Allyn and Bacon, Inc. 1987) and March, Advanced OrganicChemistry Reactions, Mechanisms, and Structures, 4th Ed., (Wiley, 1992).According to this invention, a diazonium salt is an organic compoundhaving one or more diazonium groups.

[0023] In the processes of the invention, the diazonium salt may beprepared prior to reaction with the carbon black or, more preferably,generated in situ using techniques known in the art. In situ generationalso allows the use of unstable diazonium salts such as alkyl diazoniumsalts and avoids unnecessary handling or manipulation of the diazoniumsalt. In particularly preferred processes of this invention, both thenitrous acid and the diazonium salt are generated in situ. Each of thesevariations is shown in the examples below.

[0024] A diazonium salt, as is known in the art, may be generated byreacting a primary amine, a nitrite and an acid. The nitrite may be anymetal nitrite, preferably lithium nitrite, sodium nitrite, potassiumnitrite, or zinc nitrite, or any organic nitrite such as for exampleisoamylnitrite or ethylnitrite. The acid may be any acid, inorganic ororganic, which is effective in the generation of the diazonium salt.Preferred acids include nitric acid, HNO₃, hydrochloric acid, HCl, andsulfuric acid, H₂S0₄.

[0025] The diazonium salt may also be generated by reacting the primaryamine with an aqueous solution of nitrogen dioxide. The aqueous solutionof nitrogen dioxide, NO₂/H₂O, provides the nitrous acid needed togenerate the diazonium salt.

[0026] Generating the diazonium salt in the presence of excess HCl maybe less preferred than other alternatives because HCl is corrosive tostainless steel. Generation of the diazonium salt with NO₂/H₂O has theadditional advantage of being less corrosive to stainless steel or othermetals commonly used for reaction vessels. Generation using H₂S0₄/NaNO₂or HNO₃/NaNO₂ are also relatively non-corrosive.

[0027] In general, generating a diazonium salt from a primary amine, anitrite, and an acid requires two equivalents of acid based on theamount of amine used. In an in situ process, the diazonium salt can begenerated using one equivalent of the acid. When the primary aminecontains a strong acid group, adding a separate acid may not benecessary in the processes of the invention. The acid group or groups ofthe primary amine can supply one or both of the needed equivalents ofacid. When the primary amine contains a strong acid group, preferablyeither no additional acid or up to one equivalent of additional acid isadded to a process of the invention to generate the diazonium salt insitu. A slight excess of additional acid may be used. One example ofsuch a primary amine is para-aminobenzenesulfonic acid (sulfanilicacid). Others are shown in the examples below.

[0028] In general, diazonium salts are thermally unstable. They aretypically prepared in solution at low temperatures, such as 0-5° C., andused without isolation of the salt. Heating solutions of some diazoniumsalts may liberate nitrogen and form either the corresponding alcoholsin acidic media or the organic free radicals in basic media.

[0029] However, to accomplish the process of the invention, thediazonium salt need only be sufficiently stable to allow reaction withthe carbon black. Thus, the processes of the present invention can becarried out with some diazonium salts otherwise considered to beunstable and subject to decomposition. Some decomposition processes maycompete with the reaction between the carbon black and the diazoniumsalt and may reduce the total number of organic groups attached to thecarbon black. Further, the reaction may be carried out at elevatedtemperatures where many diazonium salts may be susceptible todecomposition. Elevated temperatures may also advantageously increasethe solubility of the diazonium salt in the reaction medium and improveits handling during the process. However, elevated temperatures mayresult in some loss of the diazonium salt due to other decompositionprocesses.

[0030] The processes of the invention can be accomplished by adding thereagents to form the diazonium salt in situ, to a suspension of carbonblack in the reaction medium, for example, water. Thus, a carbon blacksuspension to be used may already contain one or more reagents togenerate the diazonium salt and the process of the inventionaccomplished by adding the remaining reagents. Some permutations of suchprocesses are shown in the examples below.

[0031] Reactions to form a diazonium salt are compatible with a largevariety of functional groups commonly found on organic compounds. Thus,only the availability of a diazonium salt for reaction with a carbonblack limits the processes of the invention.

[0032] The processes of this invention can be carried out in anyreaction medium which allows the reaction between the diazonium salt andthe carbon black to proceed. Preferably, the reaction medium is asolvent-based system. The solvent may be a protic solvent, an aproticsolvent, or a mixture of solvents. Protic solvents are solvents, likewater or methanol, containing a hydrogen attached to an oxygen ornitrogen and thus are sufficiently acidic to form hydrogen bonds.Aprotic solvents are solvents which do not contain an acidic hydrogen asdefined above. Aprotic solvents include, for example, solvents such ashexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile. For adiscussion of protic and aprotic solvents see Morrison and Boyd, OrganicChemistry, 5th Ed., pp. 228-231, (Allyn and Bacon, Inc. 1987).

[0033] The processes of this invention are preferably carried out in aprotic reaction medium, that is, in a protic solvent alone or a mixtureof solvents which contains at least one protic solvent. Preferred proticmedia include, but are not limited to water, aqueous media containingwater and other solvents, alcohols, and any media containing an alcohol,or mixtures of such media.

[0034] According to the processes of the invention, the reaction betweena diazonium salt and a carbon black can take place with any type ofcarbon black, for example, in fluffy or pelleted form. In one embodimentdesigned to reduce production costs, the reaction occurs during aprocess for forming carbon black pellets. For example, a carbon blackproduct of the invention can be prepared in a dry drum by spraying asolution or slurry of a diazonium salt onto a carbon black.Alternatively, the carbon black product can be prepared by pelletizing acarbon black in the presence of a solvent system, such as water,containing the diazonium salt or the reagents to generate the diazoniumsalt in situ. Aqueous solvent systems are preferred. Accordingly,another embodiment of the invention provides a process for forming apelletized carbon black comprising the steps of: introducing a carbonblack and an aqueous slurry or solution of a diazonium salt into apelletizer, reacting the diazonium salt with the carbon black to attachan organic group to the carbon black, and pelletizing the resultingcarbon black having an attached organic group. The pelletized carbonblack product may then be dried using conventional techniques.

[0035] In general, the processes of the invention produce inorganicby-products, such as salts. In some end uses, such as those discussedbelow, these by-products may be undesirable. Several possible ways toproduce a carbon black product according to a process of the inventionwithout unwanted inorganic by-products or salts are as follows:

[0036] First, the diazonium salt can be purified before use by removingthe unwanted inorganic by-product using means known in the art. Second,the diazonium salt can be generated with the use of an organic nitriteas the diazotization agent yielding the corresponding alcohol ratherthan an inorganic salt. Third, when the diazonium salt is generated froman amine having an acid group and aqueous NO₂, no inorganic salts areformed. Other ways may be known to those of skill in the art.

[0037] In addition to the inorganic by-products, a process of theinvention may also produce organic by-products. They can be removed, forexample, by extraction with organic solvents. Other ways may be known tothose of skill in the art.

[0038] Carbon Black Products

[0039] The reaction between a diazonium salt and a carbon blackaccording to a process of this invention forms a carbon black producthaving an organic group attached to the carbon black. The diazonium saltmay contain the organic group to be attached to the carbon black. Thus,the present invention relates to carbon black products having an organicgroup attached to the carbon black, particularly those prepared by aprocess of this invention. It may be possible to produce the carbonblack products of this invention by other means known to those skilledin the art.

[0040] The organic group may be an aliphatic group, a cyclic organicgroup, or an organic compound having an aliphatic portion and a cyclicportion. As discussed above, the diazonium salt employed in theprocesses of the invention can be derived from a primary amine havingone of these groups and being capable of forming, even transiently, adiazonium salt. The organic group may be substituted or unsubstituted,branched or unbranched. Aliphatic groups include, for example, groupsderived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones,carboxylic acids, and carbohydrates. Cyclic organic groups include, butare not limited to, alicyclic hydrocarbon groups (for example,cycloalkyls, cycloalkenyls), heterocyclic hydrocarbon groups (forexample, pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and thelike), aryl groups (for example, phenyl, naphthyl, anthracenyl, and thelike), and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl,thiazolyl, furyl, indolyl, and the like). As the steric hinderance of asubstituted organic group increases, the number of organic groupsattached to the carbon black from the reaction between the diazoniumsalt and the carbon black may be diminished.

[0041] When the organic group is substituted, it may contain anyfunctional group compatible with the formation of a diazonium salt.Preferred functional groups include, but are not limited to, R, OR, COR,COOR, OCOR, carboxylate salts such as COOLi, COONa, COOK, COO⁻NR₄ ⁺,halogen, CN, NR₂, SO₃H, sulfonate salts such as SO₃Li, SO₃Na, SO₃K, SO₃⁻NR₄ ⁺, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, PO₃H₂, phosphonatesalts such as PO₃HNa and PO₃Na₂, phosphate salts such as OPO₃HNa andOPO₃Na₂, N═NR, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SSO₃H, SSO₃ ⁻ salts, SO₂NRR′,SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl) 2-(1,3-dithiolanyl), SOR, and SO₂R. R and R′, whichcan be the same or different, are independently hydrogen, branched orunbranched C₁-C₂₀ substituted or unsubstituted, saturated or unsaturatedhydrocarbon, e.g., alkyl, alkenyl, alkynyl, substituted or unsubstitutedaryl, substituted or unsubstituted heteroaryl, substituted orunsubstituted alkylaryl, or substituted or unsubstituted arylalkyl. Theinteger k ranges from 1-8 and preferably from 2-4. The anion X⁻ is ahalide or an anion derived from a mineral or organic acid. Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂), where w is an integer from 2 to 6 and x and z areintegers from 1 to 6.

[0042] A preferred organic group is an aromatic group of the formulaA_(y)Ar—, which corresponds to a primary amine of the formulaA_(y)ArNH₂. In this formula, the variables have the following meanings:Ar is an aromatic radical such as an aryl or heteroaryl group.Preferably, Ar is selected from the group consisting of phenyl,naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl,benzothiadiazolyl, and benzothiazolyl; A is a substituent on thearomatic radical independently selected from a preferred functionalgroup described above or A is a linear, branched or cyclic hydrocarbonradical (preferably containing 1 to 20 carbon atoms), unsubstituted orsubstituted with one or more of those functional groups; and y is aninteger from 1 to the total number of —CH radicals in the aromaticradical. For instance, y is an integer from 1 to 5 when Ar is phenyl, 1to 7 when Ar is naphthyl, 1 to 9 when Ar is anthracenyl, phenanthrenyl,or biphenyl, or 1 to 4 when Ar is pyridinyl.

[0043] In the above formula, specific examples of R and R′ areNH₂—C₆H₄—, CH₂CH₂—C₆H₄—NH₂, CH₂—C₆H₄—NH₂, and C₆H₅.

[0044] Another preferred set of organic groups which may be attached tothe carbon black are organic groups substituted with an ionic or anionizable group as a functional group. An ionizable group is one whichis capable of forming an ionic group in the medium of use. The ionicgroup may be an anionic group or a cationic group and the ionizablegroup may form an anion or a cation.

[0045] Ionizable functional groups forming anions include, for example,acidic groups or salts of acidic groups. The organic groups, therefore,include groups derived from organic acids. Preferably, when it containsan ionizable group forming an anion, such an organic group has a) anaromatic group and b) at least one acidic group having a pKa of lessthan 11, or at least one salt of an acidic group having a pKa of lessthan 11, or a mixture of at least one acidic group having a pKa of lessthan 11 and at least one salt of an acidic group having a pKa of lessthan 11. The pKa of the acidic group refers to the pKa of the organicgroup as a whole, not just the acidic substituent. More preferably, thepKa is less than 10 and most preferably less than 9. Preferably, thearomatic group of the organic group is directly attached to the carbonblack. The aromatic group may be further substituted or unsubstituted,for example, with alkyl groups. More preferably, the organic group is aphenyl or a naphthyl group and the acidic group is a sulfonic acidgroup, a sulfinic acid group, a phosphonic acid group, or a carboxylicacid group. Examples of these acidic groups and their salts arediscussed above. Most preferably, the organic group is a substituted orunsubstituted sulfophenyl group or a salt thereof; a substituted orunsubstituted (polysulfo)phenyl group or a salt thereof; a substitutedor unsubstituted sulfonaphthyl group or a salt thereof; or a substitutedor unsubstituted (polysulfo)naphthyl group or a salt thereof. Apreferred substituted sulfophenyl group is hydroxysulfophenyl group or asalt thereof.

[0046] Specific organic groups having an ionizable functional groupforming an anion (and their corresponding primary amines for use in aprocess according to the invention) are p-sulfophenyl (p-sulfanilicacid), 4-hydroxy-3-sulfophenyl (2-hydroxy-5-amino-benzenesulfonic acid),and 2-sulfoethyl (2-aminoethanesulfonic acid). Other organic groupshaving ionizable functional groups forming anions are shown in theexamples below.

[0047] Amines represent examples of ionizable functional groups thatform cationic groups. For example, amines may be protonated to formammonium groups in acidic media. Preferably, an organic group having anamine substituent has a pKb of less than 5. Quaternary ammonium groups(—NR₃ ⁺) and quaternary phosphonium groups (—PR₃ ⁺) also representexamples of cationic groups. Preferably, the organic group contains anaromatic group such as a phenyl or a naphthyl group and a quaternaryammonium or a quaternary phosphonium group. The aromatic group ispreferably directly attached to the carbon black. Quaternized cyclicamines, and even quaternized aromatic amines, can also be used as theorganic group. Thus, N-substituted pyridinium compounds, such asN-methyl-pyridyl, can be used in this regard. Examples of organic groupsinclude, but are not limited to, (C₅H₄N)C₂H₅ ⁺, C₆H₄(NC₅H₅)⁺,C₆H₄COCH₂N(CH₃)₃ ⁺, C₆H₄COCH₂(NC₅H₅)⁺, (C₅H₄N)CH₃ ⁺, and C₆H₄CH₂N(CH₃)₃⁺.

[0048] An advantage of the carbon black products having an attachedorganic group substituted with an ionic or an ionizable group is thatthe carbon black product may have increased water dispersibilityrelative to the corresponding untreated carbon black. As shown in theExamples, water dispersibility of a carbon black product increases withthe number of organic groups attached to the carbon black having anionizable group or the number of ionizable groups attached to a givenorganic group. Thus, increasing the number of ionizable groupsassociated with the carbon black product should increase its waterdispersibility and permits control of the water dispersibility to adesired level. It can be noted that the water dispersibility of a carbonblack product containing an amine as the organic group attached to thecarbon black may be increased by acidifying the aqueous medium.

[0049] Because the water dispersibility of the carbon black productsdepends to some extent on charge stabilization, it is preferable thatthe ionic strength of the aqueous medium be less than 0.1 molar. Morepreferably, the ionic strength is less than 0.01 molar.

[0050] When such a water dispersible carbon black product is prepared bya process of the invention, it is preferred that the ionic or ionizablegroups be ionized in the reaction medium. The resulting product solutionor slurry may be used as is or diluted prior to use. Alternatively, thecarbon black product may be dried by techniques used for conventionalcarbon blacks. These techniques include, but are not limited to, dryingin ovens and rotary kilns. Overdrying, however, may cause a loss in thedegree of water dispersibility.

[0051] In addition to their water dispersibility, carbon black productshaving an organic group substituted with an ionic or an ionizable groupmay also be dispersible in polar organic solvents such asdimethylsulfoxide (DMSO), and formamide. In alcohols such as methanol orethanol, use of complexing agents such as crown ethers increases thedispersibility of carbon black products having an organic groupcontaining a metal salt of an acidic group.

[0052] Aromatic sulfides encompass another group of preferred organicgroups. Carbon black products having aromatic sulfide groups areparticularly useful in rubber compositions. These aromatic sulfides canbe represented by the formulas Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ orA—(CH₂)_(q)S_(K)(CH₂)_(r)Ar″ wherein Ar and Ar′ are independentlysubstituted or unsubstituted arylene or heteroarylene groups, Ar″ is anaryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substitutedaryl groups would include substituted alkylaryl groups. Preferredarylene groups include phenylene groups, particularly p-phenylenegroups, or benzothiazolylene groups. Preferred aryl groups includephenyl, naphthyl and benzothiazolyl. The number of sulfurs present,defined by k preferably ranges from 2 to 4. Particularly preferredaromatic sulfide groups are bis-para-(C₆H₄)—S₂—(C₆H₄)— andpara-(C₆H₄)—S₂—(C₆H₅). The diazonium salts of these aromatic sulfidegroups may be conveniently prepared from their corresponding primaryamines, H₂N—Ar—S_(k)—Ar—NH₂ or H₂N—Ar—S_(k)—Ar″.

[0053] Another preferred set of organic groups which may be attached tothe carbon black are organic groups having an aminophenyl, such as(C₆H₄)—NH₂, (C₆H₄)—CH₂—(C₆H₄)—NH₂, (C₆H₄)—SO₂—(C₆H₄)—NH₂.

[0054] Uses of the Carbon Black Products

[0055] The carbon black products of this invention may be used in thesame applications as conventional carbon blacks. The organic groupsattached to the carbon black, however, can be used to modify and improvethe properties of a given carbon black for a particular use. If desiredthese organic groups attached to the carbon black may also be chemicallychanged using means known in the art into other groups for a particularuse. For example, an acid group can be converted to its salt or itsamide.

[0056] Carbon black products according to the invention have beenprepared and evaluated in a number of end use applications. These usesinclude, for example, plastic compositions, aqueous inks, aqueouscoatings, rubber compositions, paper compositions and textilecompositions. The following paragraphs describe these uses generally andexamples of each are shown below.

[0057] The carbon black products of this invention may be used aspigments or colorants in a plastic material. The carbon black productsof the invention can also be used to impart conductivity to a plasticmaterial. The carbon black products of the invention may give anincreased rate of dispersion or improved quality of dispersion over thecorresponding untreated carbon blacks. These improvements offer aneconomic advantage in plastic manufacture and in value of the finishedproduct, respectively. As shown in Examples 47-62, using carbon blackproducts of the invention may improve impact strength of the plastic.Thus, the invention relates to an improved plastic compositioncomprising a plastic and a carbon black, the improvement comprising theuse of a carbon black product according to the invention.

[0058] As with conventional carbon blacks, the carbon black products canbe used with a variety of plastics, including but not limited toplastics made from thermoplastic resins, thermosetting resins, orengineered materials, for example, composites. Typical kinds ofthermoplastic resins include: (1) acrylonitrile-butadiene-styrene (ABS)resins; (2) acetals; (3) acrylics; (4) cellulosics; (5) chlorinatedpolyethers; (6) fluorocarbons, such as polytetrafluoroethylene (TFE),polychlorotrifluoroethylene (CTFE), and fluorinated ethylene propylene(FEP); (7) nylons (polyamides); (8) polycarbonates; (9) polyethylenes(including copolymers); (10) polypropylenes (including copolymers); (11)polystyrenes; (12) vinyls (polyinyl chloride); (13) thermoplasticpolyesters, such as polyethylene terephthalate or polybutyleneterephthalate; (14) polyphenylene ether alloys; and blends and alloys ofthe above with rubber modifiers. Typical thermosetting resins include:(1) alkyds; (2) allylics; (3) the aminos (melamine and urea); (4)epoxies; (5) phenolics; (6) polyesters; (7) silicones; and (8)urethanes.

[0059] Generally, the carbon black product is added like any otherpigment to the plastic used to form a plastic premix. This can be done,for example, in a dry mix or a melt stage. The carbon black products ofthe invention may be used in combination with other conventionaladditives in plastic compositions. According to the invention, the termplastic composition includes, but is not limited to, any plasticmaterial, article, goods, surface, fabric, sheet, and the like Forexample, plastic materials include automotive parts, siding for homes,liners for swimming pools, roofing materials, packaging materials, andany variety of other household or industrial items.

[0060] The carbon black products of this invention are also useful inaqueous ink formulations. The water-dispersible carbon black productsdiscussed above are particularly preferred for this use. Thus, theinvention provides an improved ink composition comprising water and acarbon black, the improvement comprising the use of a carbon blackproduct according to the invention. Other known aqueous ink additivesmay be incorporated into the aqueous ink formulation.

[0061] In general, an ink consists of four basic components: (1) acolorant or pigment, (2) a vehicle or varnish which functions as acarrier during printing, (3) additives to improve printability drying,and the like, and (4) solvents to adjust viscosity, drying and thecompatibility of the other ink components. For a general discussion onthe properties, preparation and uses of aqueous inks, see The PrintingManual, 5th Ed., Leach et al, Eds. (Chapman and Hall, 1993). Variousaqueous ink compositions are also disclosed, for example, in U.S. Pat.Nos. 2,833,736, 3,607,813, 4,104,833, 4,308,061, 4,770,706, and5,026,755.

[0062] The carbon black products of the invention, either aspredispersion or as a solid, can be incorporated into an aqueous inkformulation using standard techniques. Use of a water dispersible carbonblack product of the invention provides a significant advantage and costsavings by reducing or eliminating the milling steps generally used withother conventional carbon blacks.

[0063] Flexographic inks represent a group of aqueous ink compositions.Flexographic inks generally include a colorant, a binder, and a solvent.The carbon black products of the invention, particularly thewater-dispersible carbon products, are useful as flexographic inkcolorants. Example 101 shows the use of a carbon black product of theinvention in an aqueous flexographic ink formulation.

[0064] The carbon black products of the invention can be used in aqueousnews inks. For example, an aqueous news ink composition may comprisewater, the carbon black products of the invention, a resin andconventional additives such as antifoam additives or a surfactant.

[0065] The carbon black products of the invention may also be used inaqueous coating compositions such as paints or finishes. The use of thewater dispersible carbon black products discussed above in such coatingcompositions is preferred. Thus, an embodiment of the invention is animproved aqueous coating composition comprising water, resin and acarbon black, the improvement comprising the use of a carbon blackproduct according to the invention. Other known aqueous coatingadditives may be incorporated the aqueous coating compositions. See, forexample, McGraw-Hill Encyclopedia of Science & Technology, 5th Ed.(McGraw-Hill, 1982). See also U.S. Pat. No. 5,051,464, 5,319,044,5,204,404, 5,051,464, 4,692,481, 5,356,973, 5,314,945, 5,266,406, and5,266,361.

[0066] The carbon black products of the invention, either as apredispersion or as a solid, can be incorporated into an aqueous coatingcomposition using standard techniques. Use of a water dispersible carbonblack product provides a significant advantage and cost savings byreducing or eliminating the milling steps generally used with otherconventional carbon blacks. Examples 102 and 103 below show the use ofcarbon black products according to the invention in aqueous automotivetopcoat formulations.

[0067] The carbon black products of the invention may also be used inpaper compositions. Preferred carbon black products for this use are thewater dispersible carbon black products discussed above. Accordingly,the invention relates to an improved paper product comprising paper pulpand a carbon black, the improvement comprising the use of a carbon blackaccording to the invention.

[0068] The carbon black products of the invention, either as a solid ora predispersion, can be incorporated into paper pulp using standardpapermaking techniques as with conventional carbon blacks. Use of awater dispersible carbon black product discussed above may provide asignificant advantage and cost savings by reducing or eliminating thesteps generally used to disperse other conventional carbon blacks.Example 100 shows a paper product using a carbon black product accordingto the invention.

[0069] The paper products of the invention may incorporate other knownpaper additives such as sizing agents, retention aids, fixatives,fillers, defoamers, deflocculating agents, and the like. Advantageously,the water dispersible carbon black products discussed above are retainedmore efficiently at low loading levels when compared to the untreatedcarbon black when retention aids and acidic or alkaline sizing agentsare used.

[0070] The carbon black products of the invention may also be used, aswith conventional carbon blacks, as pigments, fillers, and reinforcingagents in the compounding and preparation of rubber compositions.Accordingly, the invention relates to an improved rubber compositioncontaining rubber and a carbon black, the improvement comprising the useof a carbon black product according to the invention. The properties ofthe carbon black are important factors in determining the performance ofthe rubber composition containing a carbon black.

[0071] Carbon blacks, for example, are useful in the preparation ofrubber vulcanizates such as those in tires. It is generally desirable inthe production of tires to utilize carbon blacks which produce tireswith satisfactory abrasion resistance and hysteresis performance. Thetreadwear properties of a tire are related to abrasion resistance. Thegreater the abrasion resistance, the greater the number of miles thetire will last without wearing out. The hysteresis of a rubber compoundmeans the difference between the energy applied to deform a rubbercompound, and the energy released as the rubber compound recovers to itsinitial undeformed state. Tires with lower hysteresis values reducerolling resistance and therefore are able to reduce the fuel consumptionof the vehicle utilizing the tire. Thus, it is particularly desirable tohave carbon black products capable of imparting greater abrasionresistance and lower hysteresis in tires.

[0072] The carbon black products of this invention are useful in bothnatural and synthetic rubber compositions or mixtures of natural andsynthetic rubbers. Carbon black products containing aromatic sulfides asthe organic group, which are discussed above, are preferred for thisuse. Particularly preferred for use in rubber compositions are carbonblack products having an attached aromatic sulfide organic group of theformula —(C₆H₄)—S_(k)—(C₆H₄)—, where k is an integer from 1 to 8, andmore preferably where k ranges from 2 to 4. The carbon black products ofthe invention can be used in rubber compositions which are sulfur-curedor peroxide-cured.

[0073] The carbon black products may be mixed with natural or syntheticrubbers by normal means, for example by milling. Generally, amounts ofthe carbon black product ranging from about 10 to about 250 parts byweight can be used for each 100 parts by weight of rubber in order toimpart a significant degree of reinforcement. It is, however, preferredto use amounts varying from about 20 to about 100 parts by weight ofcarbon black per 100 parts by weight of rubber and especially preferredis the utilization of from about 40 to about 80 parts of carbon blackper 100 parts of rubber.

[0074] Among the rubbers suitable for use with the present invention arenatural rubber and its derivatives such as chlorinated rubber. Thecarbon black products of the invention may also be used with syntheticrubbers such as: copolymers of from about 10 to about 70 percent byweight of styrene and from about 90 to about 30 percent by weight ofbutadiene such as copolymer of 19 parts styrene and 81 parts butadiene,a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of43 parts styrene and 57 parts butadiene and a copolymer of 50 partsstyrene and 50 parts butadiene; polymers and copolymers of conjugateddienes such as polybutadiene, polyisoprene, polychloroprene, and thelike, and copolymers of such conjugated dienes with an ethylenicgroup-containing monomer copolymerizable therewith such as styrene,methyl styrene, chlorostyrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine,alkyl-substituted acrylates, vinyl ketone, methyl isopropenyl ketone,methyl vinyl either, alphamethylene carboxylic acids and the esters andamides thereof such as acrylic acid and dialkylacrylic acid amide; alsosuitable for use herein are copolymers of ethylene and other high alphaolefins such as propylene, butene-1 and pentene-1.

[0075] The rubber compositions of the present invention can thereforecontain an elastomer, curing agents, reinforcing filler, a couplingagent, and, optionally, various processing aids, oil extenders, andantidegradents. In addition to the examples mentioned above, theelastomer can be, but is not limited to, polymers (e.g., homopolymers,copolymers, and terpolymers) manufactured from 1,3 butadiene, styrene,isoprene, isobutylene, 2,3-dimethyl-1,3 butadiene, acrylonitrile,ethylene, propylene, and the like. It is preferred that these elastomershave a glass transition point (Tg), as measured by DSC, between −120° C.and 0° C. Examples of such elastomers include poly(butadiene),poly(styrene-co-butadiene), and poly(isoprene).

[0076] Advantageously, the carbon black products of the presentinvention can impart improved abrasion resistance and/or reducedhysteresis to rubber compositions containing them. Examples 104-116 showthe use of carbon black products of the invention in various rubbercompositions and various properties of those compositions.

[0077] The carbon black products of this invention may also be used tocolor fibers or textiles. Preferred carbon black products for this useare the water dispersible carbon black products discussed above.Accordingly, the invention relates to improved fiber and textilecompositions comprising a fiber or textile and a carbon black, theimprovement comprising the use of a carbon black according to theinvention. Fibers suitable for use comprise natural and synthetic fiberssuch as cotton, wool, silk, linen, polyester and nylon. Textilessuitable for use comprise natural and synthetic fibers such as cotton,wool, silk, linen, polyester and nylon. Preferably natural fibers andtextiles comprising cotton, wool, silk and linen are used.

[0078] The carbon black products of the present invention may be coloredby means known in the art to color fibers and textiles with, forexample, direct and acid dyes. For a general discussion of coloring withdyes, see Kirk-Othmer Encyclopedia of Chemical Technology, Vol 8 pp280-350 “Dyes, Application and Evaluation” (John Wiley and Sons, 1979).Use of a water dispersible carbon black product discussed above providesa method for coloring these materials with a lightfast colorant.

[0079] The following examples are intended to illustrate, not limit, theclaimed invention.

EXAMPLES

[0080] Analytical Methods

[0081] Unless otherwise specified, BET nitrogen surface areas obtainedaccording to ASTM D-4820 are used for surface area measurements. CTABareas and iodine numbers are used occasionaly and were obtainedaccording to ASTM D-3765 and D-1510, respectively. DBPA data wereobtained according to ASTM D-2414.

[0082] Volatile content was determined as follows. A carbon black samplewas dried to constant weight at 125° C. A 45 mL sample of the dry carbonblack was placed in a covered 50 mL crucible that had been dried at 950°C. and heated in a muffle furnace for 7 minutes at 950° C. The volatilecontent is expressed as the percentage of weight lost by the carbonsample.

[0083] The following procedure was used in various Examples below todetermine the aqueous residue of carbon black products according to thisinvention and untreated carbon blacks. The carbon black product (5 g)was shaken with 45 g of water for 5 minutes. The resulting dispersionwas poured through a screen and rinsed with water until the washingswere colorless. A 325 mesh screen was used unless indicated otherwise.After drying the screen, the weight of residue on the screen wasdetermined and expressed as a percentage of the carbon black productused in the test.

[0084] For the Examples relating to rubber compositions, modulus,tensile strength, and elongation were determined according to ASTMD-412. Shore A hardness was determined according to ASTM D-2240-86.

[0085] The abrasion data on the rubber compositions were determinedusing an abrader which is based on a Lambourn type machine. Abrasionrates (cubic centimeter/centimeter travel) were measured at 14% and 21%slip. The slip is based on the relative velocity between the samplewheel and grindstone. In the following examples, the abrasion index isthe ratio of the abrasion rate of a control compositon divided by theabrasion rate of a rubber compostion prepared with a carbon blackproduct of the invention.

[0086] Tan δ was measured with a Rheometrics Dynamic Spectrometer ModelRDS-2 at a constant frequency of 10 Hz, a constant temperature, and inthe shear mode of strain. Strain sweeps were run from 0.2% to 120% DSA.Measurements were taken at five points per decade and the maximum Tan δwas reported.

[0087] Bound rubber was determined as follows: A 0.5 g sample of anuncured rubber composition containing a rubber and a known amount of acarbon black was placed in a wire cage and submerged in toluene at roomtemperature. After standing for one day, the sample was placed in freshtoluene, and allowed to stand for three additional days at roomtemperature. The sample was then removed, dried in an oven, and weighed.The weight of the carbon black was subtracted from weight of the samplebefore and after toluene treatment to give a value for the amount ofrubber in each sample. The weight of the sample after toluene treatment,adjusted for the weight of the carbon black and other insolubleingredients in the composition, represents the amount of insolublerubber remaining. Bound rubber was expressed as the percentage of theweight of insoluble rubber in the sample after standing in tolueneversus the amount of rubber in the original sample.

Example 1 Preparation of a Carbon Black Product with Preformed DiazoniumSalt

[0088] This example illustrates the preparation of a carbon blackproduct of the present invention. A pelleted carbon black with a surfacearea of 230 m2/g and a DBPA of 64 ml/100 g was used. An aqueous solutionof 4-bromobenzenediazonium chloride was prepared from 0.688 g of4-bromoaniline, 0.300 g of sodium nitrite, 1.38 g of concentrated HCland 2.90 g of water at <5° C. This solution was added to a suspension of10 g of the pelleted carbon black in 60 g of water at room temperature.Bubbles were released. After stirring for 60 minutes, the resultingcarbon black product was removed by filtration, washed with water andsubjected to Soxhlet extraction with tetrahydrofuran (THF) overnight.Analysis of the carbon black product after extraction showed that itcontained 2.49% bromine, compared to <0.01% for the untreated pelletedcarbon black prior to use in this example. This corresponds to 78% ofthe bromophenyl groups being attached to the carbon black product.Therefore, the carbon black product has 0.31 mmol/g of attachedbromophenyl groups.

Examples 2-4 Preparation of a Carbon Black Product with PreformedDiazonium Salt

[0089] These examples illustrate additional methods for the preparationof carbon black products of the present invention. The pelleted carbonblack used in Example 1 was used in Examples 24. An aqueous solution of4-bromobenzenediazonium chloride was prepared from 0.688 g of4-bromoaniline, 0.300 g of sodium nitrite, 1.38 g of concentrated HCland 2.90 g of water at <5° C. This solution was added to a suspension of10 g of the pelleted carbon black in 60.5 g of a 0.826% NaOH solution atthe temperature indicated. Bubbles were released. After stirring for thetime indicated in the following table, the resulting carbon blackproduct was removed by filtration, washed with water and subjected toSoxhlet extraction with THF overnight. Bromine analysis of the productafter extraction showed that a substantial fraction of the bromophenylgroups had been attached to the carbon black product. This shows thatthe preparation of carbon black products according to the invention canbe carried our at different times, temperatures and pHs. Portion ofBromophenyl bromophenyl groups, Example Temperature, C. Time, min.Bromine, % retained, % mmol/g 2 <5 5 1.88 59 0.24 3 <5 60 2.15 67 0.27 4Ambient 60 2.45 77 0.31

Example 5 Preparation of a Carbon Black Product with a Diazonium SaltGenerated in Situ

[0090] This example further illustrates the preparation of a carbonblack product of the present invention. A fluffy carbon black with asurface area of 560 m2/g, a DBPA of 90 ml/100 g and a volatile contentof 9.5% was used. Fifty grams of the fluffy carbon black were added to asolution of 8.83 g of sulfanilic acid dissolved in 420 g of water. Theresulting suspension was cooled to room temperature. Nitrogen dioxide(5.16 g) was dissolved in 30 g of ice cold water, and then added to thefluffy carbon black suspension over a period of several minutes andstirred rapidly, to produce 4-sulfobenzenediazonium inner salt in situ,which reacts with the fluffy carbon black. The resulting dispersion wasdried in an oven at 125° C., leaving only the carbon black product. Thecarbon black product contained 1.94% sulfur after Soxhlet extractionwith ethanol overnight, compared to 0.24% sulfur for the untreatedcarbon black. This corresponds to attaching 52% of the p-C₆H₄SO3— groupsto the carbon black product. Therefore, the carbon black product had0.53 mmol/g of attached p-C₆H₄SO₃— groups.

Example 6 Preparation of a Carbon Black Product

[0091] This example illustrates another method for the preparation of acarbon black product of the present invention. Sulfanilic acid (2.13 g)was dissolved in 90 g of water with stirring and heating. Ten grams of acarbon black with a CTAB surface area of 350 m2/g and a DBPA of 120ml/100 g were added. The mixture was cooled to room temperature andisobutyl nitrite (1.27 g) was added. Bubbles were released.4-Sulfobenzene diazonium hydroxide inner salt was generated in situ andit reacted with the carbon black. The mixture was stirred for 30minutes, and dried in an oven at 125° C. A sample of the resultingcarbon black product that had been subjected to Soxhlet extraction withethanol overnight contained 2.02% sulfur, compared to 0.5% for theuntreated carbon black. Therefore, the carbon black product had 0.48mmol/g of attached p-C₆H₄SO3— groups.

Example 7 Preparation of a Carbon Black Product in an Aprotic Solvent

[0092] This example illustrates the preparation of a treated carbonblack product of the present invention in an aprotic solvent. A 0.1 Msolution of tetrabutylammonium hexafluorophosphate in anhydrousacetonitrile was prepared and allowed to stand overnight over 3Amolecular sieves. A 5.4% solution of chlorobenzenediazoniumhexafluorophosphate in anhydrous acetonitrile was prepared and allowedto stand overnight over 3A molecular sieves. A carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was dried at 150° C.under nitrogen for 4 hours. The carbon black (10 g) was stirred into 80mL of the tetrabutylammonium hexafluorophosphate solution.

[0093] The diazonium solution (21 g) was added, and the mixture wasstirred for four hours. The carbon black product was recovered byfiltration and was washed with anhydrous acetonitrile. All operations upto this point were carried out in a dry box under an argon atmosphere. Asample of the carbon black product that was subjected to Soxhletextraction overnight with THF and dried had a chlorine content of 0.76%,compared to 0.02% for the untreated carbon black. Therefore, the carbonblack product had 0.21 mmol/g of attached chlorophenyl groups.

Example 8 Preparation of a Carbon Black Product in an Aprotic Solvent

[0094] This example illustrates the preparation of a treated carbonblack product of the present invention in an aprotic solvent. A carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g washeated at 950° C. under nitrogen for one hour. A 0.1 M solution oftetrabutylammonium tetrafluoroborate in anhydrous benzonitrile wasprepared and allowed to stand overnight over 3A molecular sieves. Usingglassware dried at 160° C. under argon, the carbon black (6 g) wasstirred into 50 mL of the tetrabutylammonium tetrafluoroborate solution.4-Bromobenzenediazonium tetrafluoroborate was added, and the mixture wasstirred for 15 minutes. The carbon black product was recovered byfiltration and was washed twice with anhydrous benzonitrile and twicewith hexanes. Except for the initial drying of the carbon black, alloperations up to this point were carried out under an argon atmospherein a dry box. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a bromine content of0.85%, compared to <0.01% for the untreated carbon black. Therefore, thecarbon black product had 0.11 mmol/g of attached bromophenyl groups.

Example 9 Preparation of a Carbon Black Product with a Diazonium SaltGenerated in Situ

[0095] This example illustrates another method for the preparation of acarbon black product of the present invention. A fluffy carbon blackwith a surface area of 560 m2/g, a DBPA of 90 ml/100 g and a volatilecontent of 9.5% was used. Fifty grams of the fluffy carbon black wereadded to a solution of 8.83 g of sulfanilic acid dissolved in 420 g ofwater. The resulting suspension was cooled to 30° C. and 4.6 g ofconcentrated nitric acid was added. An aqueous solution containing 3.51g of sodium nitrite was then added gradually with stirring, forming4-sulfobenzenediazonium hydroxide inner salt in situ, which reacts withthe fluffy carbon black. The resulting product was dried in an oven at125° C., leaving the carbon black product. The carbon black productcontained 1.97% sulfur after Soxhlet extraction with ethanol overnight,compared to 0.24% sulfur for the untreated fluffy carbon black. Thiscorresponds to attaching 53% of the p-C₆H₄SO₃— groups to the carbonblack product. Therefore, the carbon black product had 0.54 mmol/g ofattached p-C₆H₄SO₃— groups.

Example 10 Preparation of a Carbon Black Product with an AliphaticDiazonium Salt

[0096] This example shows another method for the preparation of a carbonblack product of the present invention. A fluffy carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was used. Twentygrams of this black were added to a solution of 4.9 g of2-aminoethanesulfonic acid in 180 g of water. Concentrated nitric acid(4.32 g) was added. A solution of 3.33 g of sodium nitrite in 15 g ofwater was added slowly with stirring, forming 2-sulfoethanediazoniumnitrate in situ, which reacted with the fluffy carbon black. A largequantity of bubbles evolved. The product was dried in an oven at 135°C., leaving a carbon black product. The resulting carbon black productcontained 1.68% sulfur after Soxhlet extraction with ethanol overnight,compared to 0.4% for the untreated fluffy carbon black. This correspondsto attaching 20% of the C₂H₄SO₃— groups to the carbon black product.Therefore, the carbon black product had 0.40 mmol/g of attached C₂H₄SO₃—groups.

Example 11 Preparation of a Carbon Black Product with a BenzyldiazoniumSalt

[0097] This example shows another method for the preparation of a carbonblack product of the present invention. A suspension of 0.676 g of4-bromobenzyl amine, 0.60 g of concentrated HCl, 30 g of water and 10.22g of the untreated carbon black used in Example 7 was prepared in an icebath. An aqueous solution containing 0.269 g of sodium nitrite was addedand the resulting suspension was stirred for 15 minutes, forming4-bromophenylmethanediazonium chloride in situ, which reacted with theuntreated carbon black. The product was filtered off, and was subjectedto Soxhlet extraction with THF overnight. The resulting carbon blackproduct contained 0.26% bromine, compared to <0.01% for the untreatedcarbon black product. This shows that 9% of the bromobenzyl groups usedin the example became attached to the carbon black product. Therefore,the carbon black product had 0.031 mmol/g of attached bromobenzylgroups.

Example 12 Preparation of a Carbon Black Product

[0098] This example illustrates the preparation of a carbon blackproduct of the present invention. Ten grams of a carbon black with asurface area of 230 m2/g and a DBPA of 70 ml/100 g was added to astirring solution of 0.8 g 4-bromobenzamide and 90 ml of acetone in 90 gof water. Concentrated HCl (0.87 g) was added followed by 0.33 g ofNaNO₂. BrC₆H₄CON₂ ⁺ was formed in situ, which reacted with the carbonblack. After stirring for 30 minutes, the mixture was allowed to standovernight and was then dried in an oven at 125° C. A sample of theproduct that had been subjected to Soxhlet extraction with THF overnightand dried contained 0.22% bromine, compared to <0.01% bromine for theunreacted carbon black.

Example 13 Preparation of a Carbon Black Product with a PreformedDiazonium Salt in a Pin Pelletizer

[0099] This example shows another method for the preparation of a carbonblack product of the present invention. A pin pelletizer was chargedwith 400 g of a fluffy carbon black with a surface area of 80 m2/g and aDBPA of 85 ml/100 g. A cold suspension of 4-sulfobenzenediazoniumhydroxide inner salt prepared from 27.1 g of the sodium salt ofsulfanilic acid, 10.32 g of sodium nitrite, 29.0 g of concentrated HCland 293.5 g of water and was added to the pelletizer. After pelletizingfor 2 minutes, the sample was removed and dried at 115° C. to constantweight. Soxhlet extraction with ethanol overnight gave a carbon blackproduct containing 1.1% sulfur, compared against 0.8% for the untreatedcarbon black. This shows that 27% of the p-C₆H₄SO₃— groups were attachedto the carbon black product. Therefore, the carbon black product had0.09 mmol/g of attached p-C₆H₄SO₃— groups.

Example 14 Preparation of a Carbon Black Product in a Pin Pelletizerwith a Diazonium Salt Generated in Situ

[0100] This example illustrates another method for preparing a carbonblack product of the present invention. A pin pelletizer was chargedwith 200 g of a carbon black with a CTAB surface area of 350 m2/g and aDBPA of 120. A solution of 44.2 g of sodium sulfanilate in 95 g of waterat 70° C. was added and the pelletizer was run for one minute. Twentygrams of water was added followed by 39.6 g of concentrated nitric acid.The pelletizer was run for an additional minute. Twenty grams of waterwas added followed by a solution of 16.76 g of sodium nitrite in 35 g ofwater, forming 4-sulfobenzenediazonium hydroxide inner salt in situ,which reacted with the carbon black. After running the pelletizer forfive minutes, a solution of 11.22 g of sodium hydroxide in 35 g of waterwas added. The pelletizer was run for an additional two minutes and theresulting a carbon black product was subsequently dried. Soxhletextraction with ethanol overnight gave a carbon black product with 3.3%sulfur, compared against 0.5% for the untreated carbon black. This showsthat 77% of the p-C₆H₄SO₃— groups were attached to the carbon blackproduct. Therefore, the carbon black product had 0.88 mmol/g of attachedp-C₆H₄SO₃— groups.

Example 15 Preparation of a Carbon Black Product in a Pin Pelletizerwith a Diazonium Salt Generated in Situ

[0101] This example further illustrates the preparation of a carbonblack product of the present invention. A pin pelletizer was chargedwith 200 g of a carbon black product with a surface area of 560 m2/g, aDBPA of 90 ml/100 g and a volatile content of 9.5%. Water (60 g),concentrated nitric acid (25.2 g), sulfanilic acid (40.4 g) and asolution of 19.7 g of sodium nitrite in 35 g of water were addedsuccessively; the pelletizer was run for one minute after each addition.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ, andit reacted with the carbon black. After standing for five minutes, theresulting carbon black product was dried at 125° C. A sample of thecarbon black product was subjected to Soxhlet extraction with ethanolovernight. It contained 2.15% sulfur compared to 0.24% for the untreatedcarbon black. This shows that 51% of the p-C₆H₄SO₃— groups were attachedto the carbon black product. Therefore, the carbon black product had0.60 mmol/g of attached p-C₆H₄SO₃— groups.

Example 16 Preparation of a Carbon Black Product in a Pelletizer with aDiazonium Salt Generated in Situ

[0102] This example illustrates another method for the preparation of acarbon black product of the present invention. A carbon black (200 g)with a CTAB surface area of 350 m2/g and a DBPA of 120 ml/100 g and 42.4g sulfanilic acid were placed in a pin pelletizer. After mixing for 40seconds, a solution of 20.7 NaNO₂ in 150 g of water was then added.4-Sulfobenzene diazonium hydroxide inner salt was formed in situ, whichreacted with the carbon black. After mixing for 45 seconds, theresulting carbon black product was dried in an oven at 120° C. A sampleof the product that had been subjected to Soxhlet extraction overnightwith ethanol contained 3.47% sulfur, compared to 0.5% sulfur for theuntreated carbon black product. Therefore, the carbon black product has0.93 mmol/g of attached p-C₆H₄SO₃— groups.

Example 17 Preparation of a Carbon Black Product in a Continuous PinPelletizer with a Diazonium Salt Generated in Situ

[0103] This example illustrates another method for preparing a carbonblack product of the present invention. A carbon black with a CTABsurface area of 133 m2/g and a fluffy DBPA of 190 ml/100 g is introducedinto a continuously operating pin pelletizer at a rate of 100 parts byweight per hour. Simultaneously, a 30% solution of sodium nitrite inwater and a suspension containing 5.43% concentrated nitric acid, 8.72%sulfanilic acid and 85.9% water are introduced into the pelletizer. Thesodium nitrite solution is introduced at 16 parts by weight per hour andthe suspension is added at 112 parts by weight per hour.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ andit reacted with the carbon black in the pelletizer. The material leavingthe pelletizer was the carbon black product. The carbon black productwas dried at 125° C. A sample of the carbon black product that had beensubjected to Soxhlet extraction with ethanol overnight contained 1.70%sulfur, compared to 0.42% for the untreated carbon black. Therefore, thecarbon black product had 0.40 mmol/g of attached p-C₆H₄SO₃— groups.

Example 18 Preparation of a Carbon Black Product with a Diazonium SaltGenerated in Situ

[0104] This example shows another method for preparing a carbon blackproduct of the present invention. In this example, the acid for thediazotization reaction comes from the amine forming the diazonium salt,sulfanilic acid. As a result, no additional acid was required.Sulfanilic acid (2.12 g) was dissolved in 90 g water at 70° C. Thesolution was added to 10 g of a carbon black with a CTAB surface area of350 m2/g and a DBPA of 120 ml/100 g, and cooled to room temperature. Asolution of 1.04 g NaNO₂ in 10 g water was added with stirring.4-Sulfobenzenediazonium hydroxide inner salt was generated in situ andit reacted with the carbon black to form the carbon black product. Afterstirring for 30 minutes, the resulting dispersion was dried in an ovenat 120° C. A sample of the carbon black product that had been subjectedto Soxhlet extraction with ethanol overnight contained 3.19% sulfur,compared to 0.5% for the untreated carbon black product. Therefore, thecarbon black product had 0.84 mmol/g of attached p-C₆H₄SO₃— groups.

Example 19 Preparation of a Carbon Black Product with a Diazonium SaltGenerated in Situ

[0105] This example illustrates another method for the preparation of acarbon black product of the present invention. In this example, the acidfor the diazotization reaction comes from the amine forming thediazonium salt, sulfanilic acid. As a result, no additional acid wasrequired. A carbon black (10 g) with a CTAB surface area of 350 m2/g anda DBPA of 120 ml/100 g was added to a boiling solution of 2.12 gsulfanilic acid in 90 g of water. A solution of 1.04 g of NaNO₂ in 10 gwater was added cautiosly. 4-Sulfobenzene diazonium hydroxide inner saltwas formed in situ, which reacted with the carbon black. After stirringfor about 20 min, the resulting dispersion was dried in an oven at 120°C. A sample of the product that had been subjected to Soxhlet extractionovernight with ethanol contained 3.16% sulfur, compared to 0.5% sulfurfor the untreated carbon black. Therefore, the carbon black product had0.83 mmol/g of attached p-C₆H₄SO3— groups.

Examples 20-30 Aqueous Dispersibility of Carbon Black Products

[0106] These examples show that carbon black products of the presentinvention described in some earlier examples are more readily dispersedin water than the corresponding untreated carbon black. Carbon BlackResidue of Carbon Residue of untreated Example Product Black Product, %control, % 20 Example 5 3.0 6 21 Example 6 0.2 97 22 Example 9 0.12 6 23Example 10 2.1 94 24 Example 13 0.07 81 25 Example 14 0.3 97 26 Example15 0.26 6 27 Example 16 0.6 97 28 Example 17 0.02 36 29 Example 18 0.0497 30 Example 19 0.01 97

Examples 31-34 Preparation and Aqueous Dispersibility of Carbon BlackProducts

[0107] These examples show that carbon black products prepared usingseveral different diazonium salts are more readily dispersed in waterthan are the corresponding untreated carbon blacks. In all cases, theuntreated carbon black used for treatment has a surface area of 230 m2/gand a DBPA of 70 ml/100 g. To prepare the carbon black product, ananiline derivative was dissolved in warm water, the untreated carbonblack (CB) was added and the mixture was cooled to room temperature.Concentrated HCl was added and then a solution of sodium nitrite inwater was added, forming a diazonium salt in situ, which reacts with theuntreated carbon black. After stirring for 15 minutes, the resultingdispersions were dried in an oven at 125° C. Residues were determinedusing the method described above. The amounts of each component andresults are shown in the following table. The untreated carbon black hada residue of 94%. Aniline Aniline HCl NaNO2 CB H20 Example derivativederivativeg g g g g Residue % 31 5-Amino 2 1.89 1.18 0.85 10.0 100 0.06Hydroxy benzene sulfonic acid 32 2-Amino 1.73 1.18 0.82 10.0 67 0.14benzene sulfonic acid 33 3- 1.72 1.18 0.84 10.4 77 0.16 Aminobenzenesulfonic acid 34 4- 2.94 2.60 0.83 10.0 71 2.0 Aminoazobenzene-4'sulfonic acid, Na salt Compara- Untreated — — — — — 94 tive

Examples 35-38 Preparation and Dispersibility of Carbon Black Products

[0108] These examples show additional carbon black products that areprepared using different diazonium salts and that are more readilydispersible in water than the corresponding untreated carbon black. Allof these examples use naphthyl diazonium salts. In all cases, a carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g wasused. A solution of 7 mmol of the naphthylamine and 0.42 g NaNO₂ in10.83 g water was cooled to <5° C. The diazonium salt was formed by theaddition of a cold (5° C.) solution of 1.63 g concentrated HCl in 1.63 gwater, maintaining the temperature at <5° C. The reaction product wasadded to a stirring slurry of 10 g of the untreated carbon black in 90 gof water. After stirring for an additional 10 minutes, the dispersionwas dried, leaving the carbon black product. Samples of the carbon blackproducts that had been subjected to Soxhlet extraction overnight withethanol were analyzed for sulfur to determine the number of attachednaphthyl groups. Naphthylamine Substitutednaphthyl Example derivativeSulfur % groups, mmol/g Residue % 35 Sodium 5-amino-2- 2.15 0.51 <0.01naphthalene sulfonate 36 4-Amino-5-hydroxy-2,7- 2.77 0.35 0.02naphthalene disulfonic acid, mono potassium salt 37 7-Amino-1,3- 3.090.40 0.01 naphthalene disulfonic acid, mono potassium salt 38 Sodium4-amino-1- 1.79 0.40 0.33 naphthalene sulfonate Compara-tive Untreated0.5 — 94

Example 39 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0109] This example illustrates another method for the preparation of acarbon black product of the present invention and illustrates that thiscarbon black product was more readily dispersible in water than is thecorresponding untreated carbon black. 7-Amino-1,3-naphthalenedisulfonicacid (1.5 g) was dissolved in 90 g warm water. Ten grams of a carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g wasadded, and the mixture was cooled to room temperature. A solution of0.42 g NaNO₂ in 5 g water was added with stirring. The diazonium saltwas formed in situ and reacted with the carbon black. Bubbles werereleased. The resulting dispersion was dried in an oven at 125° C.,giving the carbon black product. The carbon black product had a residueof 0.85%, compared to 94% for the untreated carbon black.

Example 40 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0110] This example shows that a carbon black product prepared usinganother diazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment had a surface area of 230 m2/g and a DBPA of 70 ml/100 g.5-Amino-2-hydroxy-3-sulfobenzoic acid (2.33 g), 10 g of carbon black and100 g of water were mixed in an ice bath. Cold concentrated HCl (1.18 g)was added, followed gradually by 0.85 g NaNO₂. The diazonium salt wasformed in situ, and reacted with the carbon black. After stirring for 15minutes, the resulting dispersion was dried in an oven at 125° C. toprovide the carbon black product. The 325 mesh residue of the resultingcarbon black product was 0.1%, compared to 94% for the untreated carbonblack.

Example 41 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0111] This example shows that a carbon black product prepared withanother diazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The procedure of Example 40 wasfollowed in all respects, except that 4-amino-2′-nitro-4′-sulfodiphenylamine (3.01 g) was used as the diazonium precursor. The resulting carbonblack product had a 325 mesh residue of 0.18%, compared to 94% for theuntreated carbon black.

Example 42 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0112] This example shows another preparation of a carbon black productof the present invention, and that this carbon black product was morereadily dispersible in water than is the correspondingly untreatedcarbon black. 4-Aminophenyl-phosphonic acid (0.90 g) was added to 10 gof ice cold water. NaOH (0.26 g) was added to dissolve the solid. A coldsolution of 0.42 g NaNO₂ in 5 g of cold water was added. ConcentratedHCl was added (3.83 g) and the solution was stirred at <10° C. for 15minutes, forming the corresponding diazonium salt. A cold suspension of5.02 g of a carbon black with a surface area of 230 m2/g and a DBPA of70 ml/100 g in 36.2 g of water was added and stirred for 15 minutes. Theresulting dispersion was concentrated to dryness under vacuum at roomtemperature giving a carbon black product. This carbon black productdisperses readily in water, and had a 325 mesh residue of 2.7%, comparedto 94% for the untreated carbon black. A sample of the carbon blackproduct that was dried in an oven at 125° C. did not disperse in water.A sample of the carbon black product that had been subjected to Soxhletextraction overnight with THF contained 1.57% phosphorous. Therefore,the carbon black product had 0.51 mmol/g of attached p-C₆H₄PO₃=groups.

Example 43 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0113] This example illustrates the use of a diazonium salt containing aquaternary ammonium salt in the preparation of a carbon black product ofthe present invention and the dispersibility in water of this carbonblack product. A cold solution of 3-amino-N-methylpyridinium nitrate (11mmol) in 30 g of water was added to a suspension of 11.0 g of a carbonblack (surface area 230, DBPA 70) in 70 g of water at <10° C.Concentrated HCl (2.38 g) was added. A cold solution of 0.92 g NaNO₂ in10 g water was added carefully, and the reaction mixture was stirred for20 minutes. The diazonium salt was formed in situ, and the salt reactedwith the carbon black. A solution of 0.50 g of NaOH in 10 g of water wassubsequently added. The sample was dried at 130° C., giving a carbonblack product. The carbon black product had a 325 mesh residue of 0.40%,compared to 94% for the untreated carbon black product.

Example 44 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0114] This example further illustrates the use of a diazonium saltcontaining a quaternary ammonium salt in the preparation of a carbonblack product of the present invention and the dispersibility in waterof this carbon black product. Using a procedure analogous to that ofExample 43 with 9.8 mmol 4-(aminophenyl)-trimethylammonium nitrate, 10.0g carbon black, 2.25 g concentrated HCl, 0.83 g NaNO₂, a carbon blackproduct with a 325 mesh residue of 0.6% was obtained. The residue of theuntreated carbon black was 94%.

Example 45 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0115] This example shows that a carbon black product produced withanother diazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment had a surface area of 230 m2/g and a DBPA of 70 ml/100 g. Acold (5° C.) solution of 4-carboxymethyl-benzenediazonium chloride wasprepared from 0.77 g 4-aminophenylacetic acid, 9.2 g cold water, 1.35 gcold concentrated HCl and 0.44 g NaNO₂. The diazonium solution was addedto an ice cold stirring suspension of 5.04 g of the carbon black in 35.2g of water. Bubbles were released. After stirring for 20 minutes, thedispersion was placed in a water bath at 27° C. and stirred for anadditional 20 minutes. The dispersion was dried in an oven at 120° C.,leaving the carbon black product which had a 325 mesh residue of 2.5%,compared to 94% for the untreated carbon black.

Example 46 Preparation and Aqueous Dispersibility of a Carbon BlackProduct

[0116] This example shows that a carbon black product with anotherdiazonium salt was more readily dispersible in water than thecorresponding untreated carbon black. The carbon black used fortreatment has a surface area of 230 m2/g and a DBPA of 70 ml/100 g. Apin pelletizer was charged with 200 g of the carbon black. A suspensionof 80 mmol (12.7 g) sodium 4-aminobenzoate in 45 g of water, 25.7 gconcentrated HCl, and a solution of 7.04 g NaNO₂ in 30 g of water wereadded to the pelletizer in succession, with one minute of mixing afterthe first two additions and five minutes after the last.Carboxybenzenediazonium chloride was formed in situ and it reacted withthe carbon black. A solution of 7.83 g NaOH in 30 g water was added andmixing was continued for two minutes. The resulting carbon black productwas dried at 120° C. and had a 325 mesh residue of 6.4%, compared to 94%for the untreated carbon black.

Examples 47-59 Preparation of Carbon Black Products and Their Use AsColorants in ABS

[0117] These examples illustrate the preparation of carbon blackproducts of the present invention using different amines and the use ofthese carbon black products as colorants in ABS. A fluffy carbon blackwith a surface area of 230 m2/g and a DBPA of 70 ml/100 g was used ineach example. A diazonium salt was prepared in an ice bath from thecompound indicated, 2.2 equivalents of concentrated HCl, and 1.0equivalents of NaNO₂ as a 9.65 M solution. The resulting solutions wereadded to a suspension of 200 g of the fluffy carbon black in 3L of waterand stirred for 10 to 20 minutes. The resulting carbon black product wasfiltered off, washed with water twice, and dried at about 100° C. Insome instances, the preparation was carried out by combining multiplebatches that had been made at one half or one quarter scale.

[0118] Masterbatches were prepared by fluxing 183 g ethylene-vinylacetate polymer (EVA) for one minute in a Brabender mixer at 110° C.,adding 45.8 g of the carbon black product, and mixing for fouradditional minutes. Injection molded samples for evaluation wereprepared by injection molding a mixture of 80 g of masterbatch and 1520g of ABS, (acrylonitrile-butadiene-styrene copolymer resin). The finalconcentration of the carbon black product in the molded samples is 1%.

[0119] The impact strength of the let down material was measured with anIzod impact tester; the optical properties were measured with a Huntercalorimeter. The impact strengths obtained are expressed as a percentageof the impact strength of the unfilled ABS used. Desirable propertiesare high impact strength, low Hunter L values (jetter), Hunter a valuesnear 0, and more negative Hunter b values (bluer). Generally when carbonblack is added to ABS to impart color, the impact suffers as the jetnessimproves. The results show that the carbon black products of theinvention are useful as a colorant in ABS. Impact Amount of strength,Diazonium % of Diazonium Precursor unfilled Example Precursor mmol ABSHunter L Hunter a Hunter b 47 Aniline 60 84 6.4 −0.2 −1.3 48 4-Chloro-60 87 6.6 −0.3 −1.5 aniline 49 4-Amino- 60 46 6.1 −0.3 −2.0 benzoic acid50 Ethyl 4-amino 60 71 5.3 −0.3 −1.6 benzoate 51 4-Nitro- 60 58 5.0 −0.3−1.5 aniline 52 4-Hexyl- 60 73 5.1 −0.3 −1.6 aniline 53 4-Tetradecyl- 6066 5.7 −0.3 −1.7 aniline 54 4-(N,N 60 48 5.7 −0.3 −1.7 Dimethyl amino)aniline 55 4-Amino 60 54 5.1 −0.3 −1.6 acetophenone 56 4-Amino 80 50 4.5−0.2 −1.1 phenol 57 p-Phenylene 60 45 5.2 −0.3 −1.6 diamine 58p-Phenetidine 60 63 5.1 −0.3 −1.6 59 Reference 53 5.0 −0.2 −1.6

Examples 60-62 Preparation of Carbon Black Products and Their Use AsColorants in ABS

[0120] These examples illustrate the preparation of carbon blackproducts of the present invention using different treating agents andthe use of those carbon black products as a colorant in ABS. A fluffycarbon black with a surface area of 230 m2/g and a DBPA of 70 ml/100 gwas used in each case. The procedure for Examples 47-59 was used for thepreparation of the carbon black products using 60 mmol of diazoniumprecursor.

[0121] Masterbatches were prepared by fluxing 203.6 g ABS for twominutes in a Brabender mixer with an initial temperature of 210° C.,adding 50.9 g of the carbon black product at 175° C., and mixing forthree additional minutes. Injection molded samples for evaluation wereprepared by injection molding a mixture of 75 g of masterbatch and 1425g of ABS. The final concentration of the carbon black product in themolded samples was 1%.

[0122] The impact strength of the let down material was measured with anIzod impact tester; the optical properties were measured with a Huntercalorimeter. The impact strengths obtained are expressed as a percentageof the impact strength of the unfilled ABS used. Desirable propertiesare high impact strength, low Hunter L values (jetter), Hunter a valuesnear 0, and more negative Hunter b values (bluer). Generally when carbonblack is added to ABS to impart color, the impact suffers as the jetnessimproves. The results show that carbon black products of the inventionare useful as a colorant in ABS. Impact strength, % of Example DiazoniumPrecursor unfilled ABS Hunter L Hunter a Hunter b 60 4-Aminophenol 324.5 −0.2 −1.1 61 p-Benzonitrile 37 4.4 −0.1 −1.1 62 Reference 38 4.6−0.2 −2.0

Examples 63-65 Preparation of Carbon Black Products and Their Use inColoring Polyethylene

[0123] These examples illustrate the preparation of carbon blackproducts of the present invention. A carbon black with a surface area of140 m2/g and a DBPA of 114 ml/100 g was used. Cold solutions oftetradecylbenzenediazonium chloride were prepared fromtetradecylaniline, concentrated HCl, NaNO₂, isopropanol and water. Thediazonium solution was added to 200 g carbon black in a pin pelletizerand mixed for the indicated time. Additional water #1 was added andmixing was continued for three more minutes. After addition of morewater #2 and isopropanol #2 and further mixing, the resulting carbonblack product was dried in an oven. A control sample was prepared bymixing the untreated carbon black in the same pelletizer with water andisopropanol, and drying.

[0124] Masterbatches were prepared by mixing 169.34 g low densitypolyethylene with 72.6 g of a carbon black sample in a Brabender mixerat 85° C. for five minutes. Plaques for evaluation were prepared byinjection molding a mixture of 10 g of masterbatch and 1490 g of highdensity polyethylene. The final concentration of carbon black productwas 0.2%. The optical properties of the plaques were measured with aHunter calorimeter. The results show that the carbon black products weresomewhat jetter (lower Hunter L values) than the control and are usefulas a colorant for polyethylene. Example 63 Example 64 Example 65Precursor 4-Tetra- 4-Tetra- none decylaniline decylaniline Precursoramount, g 6.95 11.56 — HCl, g 4.67 7.79 — H2O, g 27 48 — Isopropanol, g25 25 — NaNO2, g 2.07 3.45 — Initial mix time, min 3 1 — Added water #1,g 170 130 — Added water #2, g 5 5 263 Added isopropanol #2, g — 5 20Final mix time, min 1 2 5 Hunter L 6.9 6.7 7.1 Hunter a −0.2 −0.3 −0.3Hunter b 0.3 0.0 0.2

Example 66 Preparation of a Carbon Black Product in a Pelletizer

[0125] This example illustrates the preparation of a carbon blackproduct of the present invention. A pelletizer was charged with 300 g ofa carbon black with a surface area of 254 m2/g and a DBPA of 188 ml/100g and 21.2 g of sulfanilic acid. After mixing for 45 seconds, 220 g ofwater was added. After mixing for 20 seconds, 13.2 g of concentratednitric acid was added. After mixing for an additional 20 seconds, asolution of 10.3 g of NaNO₂ in 270 g of water was added. After mixingfor 2 minutes, the resulting carbon black product was dried in an ovenat 125° C.

Example 67 Use of a Carbon Black Product in Polypropylene

[0126] This example illustrates the use of a carbon black product of thepresent invention in polypropylene to impart conductivity to thepolypropylene. A mixture of 263.1 g of the carbon black product ofExample 66 and 881 g of polypropylene was added to a Banbury mixer at66° C. and mixed for 5 minutes. A sample of the material was let down toa 20% carbon black product content on a two roll mill by mixing withadditional polypropylene. The product had a resistivity of 68 ohm-cm,compared to 64 ohm-cm for a similar product made with the untreatedcarbon black used in Example 66.

Examples 68-76 Preparation of Carbon Black Products

[0127] These examples show other diazonium compounds that can be used toprepare carbon black products of the present invention. The diazoniumcompounds encompass a range of substitution patterns on the aromaticring and with various electron-withdrawing or electron-donatingsubstituents. In each case, a cold diazonium salt solution was preparedfrom the indicated aryl amine, NaN0₂ and either concentrated HCl orHNO₃. The diazonium solution was added to a suspension of carbon blackin water and/or stirred for 15 to 20 minutes. The resulting carbon blackproduct was isolated by filtration, washed with water, and subjected toSoxhlet extraction with THF overnight. The analyses shown below reportincreases from the reaction over the level contained in the appropriateuntreated carbon black. The results show that a substantial fraction ofthe organic groups are attached to the carbon black product. CarbonCarbon black black Substituted product product Treatment Fraction ofphenyl Surface Area DBPA Level, CI Analysis N Analysis bonded groupsgroups Example Aryl amine m2/g ml/100 g μmol/g CB μmol/g μmol/g as %μmol/g 68 4-Chloro aniline 230 64 300 196 — 65 196 69 4-Chloro-3-methyl230 64 300 215 — 72 215 aniline 70 4-Chloro-2-methyl 230 64 300 170 — 57170 aniline 71 4-Chloro -3-nitro 230 64 300 209 — 70 209 aniline 724-Chloro-2-nitro 230 64 300 123 — 41 123 aniline 73 Sodium 3 Amino 23064 300 64 — 21 64 6-chloro benzene sulfonate 74 3-Amino Pyridine 350*120 580 — 461 79 461 75 4-Amino benzonitrile 230 70 300 — 263 88 263 764-Bromo-2-chloro 230 70 407 264 — 65 264 aniline

Example 77 Preparation of a Carbon Black Product Containing Aryl andAlkoxy Groups

[0128] This example illustrates the preparation of a carbon blackproduct containing aryl and alkoxy groups. A dry sample of a carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g wasused. Bromoethanol (30 ml) was added to a mixture of 3 g of the carbonblack and 0.34 g of dry chlorobenzenediazonium hexafluorophosphate.Bubbles were released rapidly. After stirring for 30 minutes, theresulting carbon black product was filtered, subjected to Soxhletextraction overnight with THF and dried. The carbon black productcontained 0.58% Cl and 0.84% Br compared to 0.02% Cl and <0.01% Br forthe untreated carbon black product. The carbon black product thereforehad 0.16 mmol/g of attached chlorophenyl groups and 0.11 mmol/g ofattached bromoethoxy groups.

Example 78 Preparation of a Carbon Black Product Containing Aryl andAlkoxy Groups

[0129] This example illustrates the preparation of a carbon blackproduct containing aryl and alkoxy groups. A dry sample of a carbonblack with a surface area of 230 m2/g and a DBPA of 70 ml/100 g wasused. Chloroethanol (30 ml) was added to a mixture of 3 g of the carbonblack and 0.32 g of dry bromobenzenediazonium tetrafluoroborate. Bubbleswere released rapidly. After stirring for 30 minutes, the resultingcarbon black product was filtered, subjected to Soxhlet extractionovernight with THF and dried. The carbon black product contained 0.58%Cl and 0.84% Br compared to 0.02% Cl and 0.01% Br for the untreatedcarbon black. The carbon black product therefore had 0.16 mmol/g ofattached bromophenyl groups and 0.11 mmol/g of attached chloroethoxygroups.

Example 79 Preparation of a Carbon Black Product Containing Aryl andAlkoxy Groups

[0130] This example illustrates another method for the preparation of acarbon black product containing aryl and alkoxy groups. A carbon blackwith a surface area of 230 m2/g and a DBPA of 70 ml/100 g was used. Asolution of 4-bromobenzene diazonium nitrate was prepared in an ice bathfrom 0.69 g bromoaniline, 0.33 g NaNO₂, 0.86 g concentrated HNO₃ and ca.3 ml of water. The diazonium solution was added to a suspension of 10 gcarbon black product, 5 g chloroethanol and 85 g water that was stirringat room temperature. After stirring for 30 minutes, the carbon blackproduct was removed by filtration, washed with THF, and dried in an ovenat about 125° C. A sample that had been subjected to Soxhlet extractionovernight with THF contained 1.08% bromine and 0.16% chlorine. A controlcarbon black sample was prepared by stirring the same untreated carbonblack in a 5.6% chloroethanol/water solution, washing with THF, dryingand extracting with THF. The control contained 0.02% bromine and 0.082%chlorine. The carbon black product therefore had 0.13 mmol/g of attachedbromophenyl groups and 0.022 mmol/g of attached chloroethoxy groups.

Example 80 Preparation of a Carbon Black Product

[0131] This example further illustrates the preparation of a carbonblack product of the present invention. Concentrated HCl (16.2 g) wasdiluted with 40 g water and added to 9.30 g 4-aminophenyldisulfide. Themixture was stirred in an ice bath. A cold solution of 6.21 g NaNO₂ in30 g water was added with stirring, keeping the mixture below 10 C.4-Diazophenyl disulfide dichloride is formed. The mixture was added to asuspension of 250 g of pelleted carbon black (iodine number of 120 mg/gand a DBPA of 125 ml/100 g) in 1.3L of water at 10° C. with stirring.Bubbles were released. After stirring for 2 ½ hours, the product isfiltered, washed with ethanol, washed with additional water and thendried at 125° C. to a constant weight. A sample of the carbon blackproduct that was extracted overnight with THF and dried contained 1.75%sulfur, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.10 mmol/g of attached dithiodi-4,1-phenylenegroups.

Example 81 Preparation of a Carbon Black Product

[0132] This example illustrates the preparation of a carbon blackproduct of the present invention. Concentrated HCl (5.4 g) was dilutedwith 40 g water and added to 3.1 g 4-aminophenyldisulfide. The mixturewas stirred in an ice bath, and 50 g additional cold water was added. Acold solution of 2.07 g NaNO₂ in 30 g water was added with stirring,keeping the mixture below 10° C. 4-Diazophenyl disulfide dichloride wasformed. The mixture was added to a suspension of 125 g of pelletedcarbon black (iodine number of 120 mg/g and a DBPA of 125 ml/100 g) inabout 800 g of water at 10-15° C. with stirring. Bubbles were released.After stirring for 2 hours, the resulting carbon black product wasfiltered, washed with ethanol, washed with additional water and thendried at 125° C. to a constant weight. A sample of the carbon blackproduct that was extracted overnight with THF and dried contained 1.56%sulfur, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.075 mmol/g of attached dithiodi-4,1-phenylenegroups.

Example 82 Preparation of a Carbon Black Product

[0133] This example further illustrates the preparation of a carbonblack product of the present invention. A pelleted carbon black with aniodine number of 120 mg/g and a DBPA of 125 ml/100 g was used. Butyllithium (50 mL of a 1.0 M solution in hexane) was added to 200 mL of dryDMSO under nitrogen. A solution of 11.1 g of 4-aminophenyl disulfide in100 mL dry DMSO was prepared and added under nitrogen with cooling froman ice bath. A dark violet colored developed. S₂Cl₂ (3.3 mL) was addedover 10 minutes with stirring and continued cooling. A solution of 1.7 gNaOH in water was added. After addition of more water, the product wasextracted with 450 mL of ether. The ether was removed under vacuum, andthe residue was dissolved in CH₂Cl₂, washed with water, dried andconcentrated under vacuum to give 4-aminophenyltetrasulfide as an oil.

[0134] 4-Aminophenyl tetrasulfide (5.85 g) was stirred with 150 g ofwater in an ice bath. A cold solution of 8.1 g concentrated HCl in 50 gwater was added, followed gradually by a solution of 3.2 g NaNO₂ in 40 gwater, forming 4-diazophenyl tetrasulfide dichloride. After stirring,the resulting suspension was added to a stirring slurry of 125 g of thepelleted carbon black in about 800 g of water. Bubbles were released.After stirring for 2 ½ hours, the resulting carbon black product wasfiltered off, washed with ethanol, washed with water and dried at 140°C. A sample of the carbon black product that had been extracted with THFovernight and dried contained 1.97% sulfur, compared to 1.08% for theuntreated black. Therefore, the carbon black product had 0.07 mmol/g ofattached tetrathiodi-4,1-phenylene groups.

Example 83 Preparation of a Carbon Black Product

[0135] This example illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 ml/100 g was used. A cold solution of 2.65g concentrated HCl and 30 g water was added to a mixture of 2.85 g4-aminophenyl phenyl disulfide in 50 g water that was stirring in an icebath. A cold solution of 1.04 g NaNO₂ in 30 g of water was added over aperiod of 10 minutes. 4-Diazophenyl phenyl disulfide chloride wasformed. The diazonium suspension was added to a suspension of 122 gcarbon black in about 800 g water that was stirring at 15° C. Bubbleswere released. After stirring for about two hours, the carbon blackproduct was filtered off, washed with isopropanol, washed with water,and dried in an oven at about 125° C. A sample of the carbon blackproduct that had been subjected to Soxhlet extraction overnight with THFand dried had a sulfur content of 1.32%, compared to 1.08% for theuntreated carbon black. Therefore, the carbon black product had 0.038mmol/g of attached phenyldithiophenylene groups.

Example 84 Preparation of a Carbon Black Product

[0136] This example further illustrates the preparation of a carbonblack product of the present invention. Nitrogen dioxide (4.1 g) wasbubbled into 40 g water that was cooled in an ice bath. The resultingsolution was added slowly to a cold (10° C.), stirring suspension of4.65 g of 4-aminophenyl disulfide in 100 g water. The resulting solutionof 4-diazophenyl disulfide dinitrate was added to a cold stirringsuspension of 125 g of carbon black (iodine number of 120 mg/g and aDBPA of 125 ml/100 g) in 800 g cold (12-14° C.) water. The reactionmixture was stirred for 3 days, and allowed to warn to room temperaturein the process. The resulting carbon black product was recovered byfiltration and was dried. A sample of the carbon black product extractedwith THF overnight had 1.81% sulfur, compared to 1.07% sulfur in theuntreated carbon black product. Therefore, the carbon black product had0.12 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 85 Preparation of a Carbon Black Product

[0137] This example further illustrates the preparation of a carbonblack product of the present invention. The procedure of Example 80 wasfollowed, except that a carbon black with an iodine number of 90 mg/gand a DBPA of 114 ml/100 g was used, and except that an additional 50 mlof water was used to form the aminophenyl disulfide dihydrochloridesuspension. A sample of the resulting carbon black product that had beenextracted overnight with THF and dried contained 2.12% sulfur, comparedto 1.45% for the untreated carbon black. Therefore, the carbon blackproduct had 0.10 mmol/g of attached dithiodi-4,1-phenylene groups.

Example 86 Preparation of a Carbon Black Product

[0138] This example illustrates the preparation of a carbon blackproduct of the present invention. A carbon black with an iodine numberof 120 mg/g and a DBPA of 125 ml/100 g was used. A cold solution of4-diazo-2-chlorophenyl disulfide dichloride was prepared by adding acold solution of 3.59 g of NaNO₂ in 40 g water to a suspension of 6.6 g4-amino-2-chlorophenyl disulfide, 9.12 g concentrated HCl and about 150g water that was stirring in an ice bath. After stirring for fiveminutes, the diazonium solution was then added to a stirred suspensionof 140 g of carbon black in 1 liter of water at 10-14° C. After stirringfor two hours, the resulting carbon black product was filtered off,washed with ethanol, washed with water, and then dried in an oven at125° C. A sample of the carbon black product that was subjected toSoxhlet extraction overnight with THF and dried had a sulfur content of1.60%, compared to 1.08% for the untreated carbon black. Therefore, thecarbon black product had 0.081 mmol/g of attacheddithiodi-4,1-(3-chlorophenylene) groups.

Example 87 Preparation of a Carbon Black Product with a Diazonium SaltGenerated in Situ

[0139] This example illustrates the preparation of a carbon blackproduct of the present invention with a diazonium salt that is generatedin situ. A carbon black with an iodine number of 120 mg/g and a DBPA of125 ml/100 g was used. 4-Aminophenyl disulfide (8.38 g) was dissolved ina solution of 14.65 g of concentrated HCl and about 150 g of water, andadded to a stirred slurry of 225 g of carbon black in about 1.4 L ofwater. A solution of 5.28 g NaNO₂ in about 50 g water was added, forming4-diazophenyl disulfide in situ, which reacted with the carbon black.After stirring for two hours, the resulting carbon black product wasremoved by filtration, washed with ethanol, washed with water, and driedat about 125° C. A sample of the carbon black product that had beensubjected to Soxhlet extraction overnight with THF and dried contained1.89% sulfur, compared against 1.08% for the untreated carbon black.Therefore, the carbon black product had 0.13 mmol/g of attacheddithiodi-4,1-phenylene groups.

Example 88 Preparation of a Carbon Black Product

[0140] A carbon black product having attached dithiodi-4,1-phenylenegroups was prepared by following the method of Example 80 and using asuspension of 8.38 g 4-aminophenyl disulfide in about 100 g of water, asolution of 13.65 g concentrated HCl in 40 g of water, a solution of5.04 g NaNO₂ in 30 g of water, and a slurry of 225 g of the same carbonblack in 1.4 L of water. The carbon black slurry was stirred at 10-14°C. when the diazonium solution was added.

Examples 89 and 90 Comparative Carbon Black Products

[0141] In these comparative examples, the carbon blacks used in Examples80 and 85 were washed with water, ethanol and water, and subsequentlydried to give the comparative carbon black products of Examples 88 and89, respectively.

Examples 91-99 Use of Different Carbon Blacks for the Preparation ofCarbon Black Products that are Water Dispersible

[0142] This example shows the use of a variety of carbon blacks in thepreparation of carbon black products of the present invention. Thisexample also shows that the carbon black products were more readilydispersible in water than the corresponding unreacted carbon blacks.Sulfanilic acid was dissolved in 200 g of hot water. The carbon blackproduct (30 g) was added and the mixture was allowed to cool to 25 to30° C. Concentrated HCl was added (2.15 equivalents based on thesulfanilic acid used) and then a 9.65M solution of NaNO₂ in water wasadded (1.2 equivalents based on the sulfanilic acid used), forming4-sulfobenzenediazonium hydroxide in situ, which reacted with the carbonblack. After stirring for 30 minutes, the resulting dispersion was driedin an oven at 100° C., giving the resulting carbon black product.Original Original Carbon black Residue of Carbon product Residue of auntreated Black Surface DBPA Sulfanilic acid carbon black carbon blackExample Area m2/g ml/100g g product, % product, % 91   350** 120 6.981.0 97 92  140 114 3.03 0.6* 45 93 1500 330 32.55 0.6* 35 94  42 1210.91 0.1 26 95  80 85 1.73 <0.1 81 96  24 132 0.44 4.6 31 97  24 1321.50 0.2 31 98  254 178 5.43 <0.1 23 99  18 39 0.93 4.4 40

Example 100 Preparation of a Carbon Black Product and Its Use in thePreparation of Black Paper

[0143] This example shows the preparation of a carbon black product ofthe present invention and the use of that product in the preparation ofblack paper. A carbon black (300 g) with a surface area of 80 m2/g and aDBPA of 85 ml/100 g was added to a pin pelletizer with 18.2 g ofsulfanilic acid. After mixing briefly, 150 g of water, 11.2 g ofconcentrated nitric acid, 30 g of water and a solution of 8.78 g ofNaNO2 in 35 g of water were added in succession with 15 seconds ofmixing after each addition. 4-Sulfobenzenediazonium hydroxide inner saltwas formed in situ and it reacted with the carbon black. The resultingcarbon black product was dried in an oven at 125° C. A dispersion ofthis carbon black product was prepared by dispersing it in water in alaboratory homogenizer for 30 seconds.

[0144] A comparative dispersion was made by grinding 200 g of the sameunreacted carbon black in a solution of 7 g of a lignosulfonatedipsersant, 5 ml concentrated NH₄OH and 770 g water with grinding mediain a ball mill for 4 hours, at which point a Hegman gauge reading of 7was obtained.

[0145] Penobscott bleached hardwood kraft pulp (160 g) and St. Felicianbleached softwood kraft pulp (240 g) were dispersed in water in a Cowlesdissolver. The stock solution was transferred into a TAPPI standardlaboratory beater and diluted to a volume of 23 liters. The stocksolution was circulated in the beater for five minutes, and then placedunder load and beaten for 50 minutes to a corrected Canadian StandardFreeness of 355 ml.

[0146] Sufficient pulp to make three 2.75 g hand sheets was diluted to3L, and the appropriate amount of carbon black dispersion wasincorporated. A suspension was prepared for each carbon black loadinglevel. Each suspension was divided into three portions. The firstportion was used as is. Rosin and alum were added to the second portionat the rates of 80 pounds and 60 pounds per bone dry ton, respectively.HERCON 79 (AKD) size and BL 535 retention aid were added to the thirdportion at the rates of four pounds and three pounds per bone dry ton,respectively. One 8″×8″ Noble & Wood handsheet was made from eachsample. The resulting handsheets were evaluated for TAPPI brightnessusing 45°/0° geometry.

[0147] HERCON is a registered trademark for sizes produced and sold byHercules Inc., Wilmington DE. BL 535 is available from BuckmanLaboratories, Inc., Memphis Tenn.

[0148] The following table shows the brightness of handsheets made withthe carbon black product dispersion and with the control dispersion.These data show that the carbon black product can be used to colorpaper. These data also show that when the paper was made with an acidicrosin size and an alum retention aid, the carbon black product wasretained more efficiently and advantageously at low loading levels whencompared against the unreacted carbon black. These data further showthat when the paper was made with an alkaline AKD size and BL 535retention aid, the carbon black product was retained more efficientlyand advantageously at low loading levels when compared against theunreacted carbon black. Carbon black product, Brightness, Brightness,pounds per Treated carbon Untreated carbon bone dry ton None AKD Alumblack product black product 10 X 67 69 46 50 15 X 67 67 43 50 25 X 59 6134 41 50 X 44 47 18 24 100 X 33 36 9 13 200 X 20 23 0 5 10 X 16 18 21 2315 X 12 13 19 21 25 X 11 13 14 16 50 X 7 8 10 11 100 X 7 7 7 8 200 X 4 55 5 10 X 16 20 22 24 15 X 13 16 19 21 25 X 11 12 13 14 50 X 8 10 9 11100 X 7 9 6 7 200 X 6 8 4 5

Example 101 Use of a Carbon Black Product in the Preparation of AnAqueous Ink

[0149] This example illustrates the advantages of using a carbon blackproduct of the present invention in an aqueous ink formulation. Inkcomposition A was prepared by adding 3.13 parts of the carbon blackproduct of Example 13 to a vehicle made by mixing 2.92 parts JONCRYL61LV resin, 0.21 parts isopropanol, 0.31 parts ARROWFLEX defoamer, 7.29parts JONCRYL 89 resin and 6.98 parts water, and shaking the compositionfor 10 minutes on a paint shaker. The table below shows the 635 meshresidue level.

[0150] JONCRYL is a registered trademark for resins produced and sold bySC Johnson Polymer, Racine, Wis. ARROWFLEX is a registered trademark fordefoamers produced and sold by Witco, New York, N.Y.

[0151] Ink composition B was prepared by grinding a mixture of 120 partsof the carbon black product used in Example 13, 112 parts of JONCRYL61LV resin, 8 parts of isopropanol, 4 parts of ARROWFLEX defoamer, 156parts of water and 400 g of grinding media. In order to check the grindlevel, samples were periodically let down to composition C thatcontained 15.0 parts carbon black product, 14.0 parts JONCRYL 61LVresin, 1.0 parts isopropanol, 1.7 parts ARROWFLEX DEFOAMER, 35.1 partsJoncryl 89 and 33.4 parts water.

[0152] Ink composition D was prepared by grinding a mixture of 120 partsof the untreated carbon black used in Example 13, 112 parts of JONCRYL61LV resin, 8 parts of isopropanol, 4 parts of ARROWFELX defoamer, 156parts of water and 400 g of grinding media. In order to check the grindlevel, samples were periodically let down to composition E thatcontained 15.0 parts carbon black product, 14.0 parts JONCRYL 61LVresin, 1.0 parts isopropanol, 1.7 parts ARROWFLEX defoamer, 35.1 partsJONCRYL 89 resin and 33.4 parts water.

[0153] The residues from ink compositions A, C and E as a function ofgrinding time are provided in the following table, and clearly show thata carbon black product of the present invention disperses more readilythan the corresponding unreacted carbon black in these aqueous inks. InkA Ink C Ink E 635 Mesh 635 Mesh 635 Mesh Dispersion time Residue, %Residue, % Residue, % 10 Minutes shaking 2.6 — — 20 Minutes Ball Mill —0.3 — 40 Minutes Ball Mill — 0.2 — 1 Hour Ball Mill — 0.02 about 100  2Hours Ball Mill — — 10.8  3 Hours Ball Mill — — 5.8  4 Hours Ball Mill —— 0.9 10 Hours Ball Mill — — 0.5 14 Hours Ball Mill — — 0.3 15 HoursBall Mill — — 1.0 16 Hours Ball Mill — — 1.0

Example 102 Use of a Carbon Black Product in the Preparation of anAqueous Coating

[0154] This example shows that carbon black products of the presentinvention are useful for the preparation of aqueous coatings. The carbonblack product from Example 9 (10 g) was dispersed in 90 g of water bystirring for 10 minutes. Coating composition A was prepared by stirring4.3 g of this dispersion into a mixture of 7.53 g of CARGILL 17-7240acrylic resin, 0.80 g of dimethylethanolamine (DMEA), 19.57 g water,0.37 g SURFYNOL CT136 surfactant, 1.32 g CARGILL 23-2347 melamine resin,0.53 g ethylene glycol monobutyl ether and 0.075 g BYK-306 surfactant.CARGILL 17-7240 acrylic resin and CARGILL 23-2347 melamine resin areavailable from Cargill Inc., Minneapolis, Minn. SURFYNOL CT136 is aregistered trademark for surfactants produced and sold by Air Productsand Chemicals, Inc., Allentown, Pa. BYK-306 is a registered trademarkfor surfactants produced and sold by BYK-Chemie USA, Wallingford.

[0155] A millbase was prepared by grinding an oxidized carbon blackproduct (15 g) with a surface area of 560 m2/g, a DBPA of 80 ml/100 gand a volatile content of 9% in a mixture of 74.6 g of CARGILL 17-7240acrylic resin, 9.53 g DMEA, 236.5 g water and 16.35 g CT-136 surfactantuntil its mean volume particle size was 0.18 microns. Comparativecoating composition B was prepared by mixing 24.4 g of this millbasewith a mixture of 17.51 g CARGILL 17-7240 acrylic resin, 1.74 g DMEA,50.56 g water, 3.97 g CARGILL 23-2347 melamine resin, 1.59 g ethyleneglycol monobutyl ether and 0.23 g BYK-306 surfactant. Glossy lenettapaper coated with compositions A and B was dried at 3500F for 10minutes. A clear coat was applied, and the samples were dried again. Thepaper coated with composition A had Hunter L,a,b values of 1.0, 0.01 and0.03, respectively, compared to 1.1, 0.01 and -0.06, respectively forthe paper coated with comparative composition B.

Example 103 Preparation of a Carbon Black Product and Its Use in anAqueous Coating

[0156] This example illustrates the preparation of a carbon blackproduct of the present invention and the use of this carbon blackproduct in an aqueous coating. A carbon black (200 g ) with a CTABsurface area of 350 m2/g and a DBPA of 120 ml/100 g was added to astirred solution of 42.4 g sulfanilic acid in 2800 g of water. Nitrogendioxide (25.5 g) was dissolved in 100 g of cold water and added to thecarbon black product suspension. Bubbles were released.4-Sulfobenzenediazonium hydroxide inner salt was formed in situ, whichreacted with the carbon black. After stirring for one hour, 5 g ofadditional NO₂ was added directly to the carbon black dispersion. Thedispersion was stirred for an additional 15 minutes, and left overnight.The resulting carbon black product was recovered by drying thedispersion in an oven at 130° C.

[0157] A dispersion of this carbon black product was prepared bystirring 10 g of the carbon black product in 90 g of water. Coatingcomposition C was prepared by stirring 4.3 g of this dispersion into amixture of 7.53 g of CARGILL 17-7240 acrylic resin, 0.80 g of DMEA,19.57 g water, 0.37 g SURFYNOL CT136 surfactant, 1.32 g CARGILL 23-2347melamine resin, 0.53 g ethylene glycol monobutyl ether and 0.075 gBYK-306 surfactant.

[0158] A millbase was prepared by grinding (in an attritor) an oxidizedcarbon black product (15 g) with a surface area of 560 m2/g, a DBPA of91 mL/100 g and a volatile content of 9.5% in a mixture of 74.6 g ofCARGILL 17-7240 acrylic resin, 9.53 g DMEA, 236.5 g water and 16.35 gSURFYNOL CT-136 surfactant for 24 hours. Comparative coating compositionD was prepared by mixing 24.4 g of this millbase with a mixture of 17.51g CARGILL 17-7240 acrylic resin, 1.74 g DMEA, 50.56 g water, 3.97 gCARGILL 23-2347 melamine resin, 1.59 g ethylene glycol monobutyl etherand 0.23 g BYK-306 surfactant.

[0159] Glossy lenetta paper coated with compositions A and B was driedat 350° F. for 10 minutes. A clear coat was applied, and the sampleswere dried again. The paper coated with composition C had Hunter L, a,and b values of 1.0, 0.01 and 0.03, respectively, compared to 1.1, 0.01and -0.06, respectively for the paper coated with comparativecomposition D.

Examples 104-108 Use of Carbon Black Products in Rubber Formulations

[0160] This example illustrates the use of the carbon black products ofexamples 80 to 84 and the comparative example 89 in rubber formulations.The polymer is milled in a Brabender mixer for 1 minute at 100° C. Amixture of ZnO and the carbon black product was added and mixed for 2additional minutes. The stearic acid and FLEXZONE 7P anti-degradant wereadded and mixed for 2 additional minutes. The sample was dumped, cooledand mixed at 80° C. for 1 minute, the curatives were added, and themixing was continued for an additional minute. The sample was thenpassed through a two roll mill three times. The recipes and performancedata in each case are given in the tables below. NS 114 is a chemicallymodified tin coupled solution SBR available from Nippon Zeon, Japan.FLEXZONE is a registered trademark for antidegradant products availablefrom Uniroyal Chemical, Naugatuck, Conn. Example 104 105 106 107 108Comparative NS 114 100 100 100 100 100 100 CB Product 50 Example 80 CBProduct 50 Example 81 CB Product 50 Example 82 CB Product 50 Example 83CB Product 50 Example 84 Control CB 50 Example 89 ZnO 3 3 3 3 3 3Stearic Acid 2 2 2 2 2 2 FLEXZONE 1 1 1 1 1 1 7P product CBS* 1.25 1.251.25 1.25 1.25 1.25 MBT** 0.2 0.2 0.2 0.2 0.2 0.2 Sulfur 1.75 1.75 1.751.75 1.75 1.75 Total 159.2 159.2 159.2 159.2 159.2 159.2

[0161] 100% 300% Abrader Abrader Modulus Modulus Tensile Hardness BoundTan δ Tan δ index index Mpa Mpa Mpa Elong. % Shore A rubber % 0° C. 70°C. 14% slip 21% slip Example 104 4.18 — 19.5 290 60 44.5 0.244 0.114 122142 Example 105 3.93 — 16.7 274 60 39.6 0.265 0.137 114 141 Example 1064.33 19.1 20.9 314 61 35.2 0.277 0.131 110 132 Example 107 3.44 15.219.6 372 61 30.8 0.304 0.170 103 105 Example 108 3.67 17.6 19.6 335 6040.9 0.251 0.122 113 129 Comparative 3.25 14.1 18.4 385 60 28.1 0.3270.173 100 100

[0162] These data show that carbon black products of the presentinvention are useful in rubber formulations. They further show thatsignificant increases in modulus, bound rubber and abrasion resistanceare obtained, as are significant decreases in Tan δ. The magnitude ofthe effect depends on the treatment level as well as on the specificgroups attached to the carbon black product.

[0163] Examples 109-112

Use of a Carbon Black Product in Rubber Formulations

[0164] This example illustrates the use of a carbon black product of thepresent invention in several different rubber formulations. Rubbercompounds were prepared from the carbon black product of Example 85 andof the comparative carbon black product of Example 90 by the methoddescribed for examples 104-108 using the recipes below. DURADENE 715 isa solution SBR. DURADENE is a registered trademark for SBR productsavailable from Firestone, Akron Ohio. Example 109 Comparative 110Comparative 111 Comparative 112 Comparative SBR 100 100 1500 Duradene715100 100 50 50 NR 100 100 50 50 CB Product 50 50 50 50 Example 85 Control50 50 50 50 CB Example 90 ZnO 3 3 3 3 4 4 3 3 Stearic 2 2 2 2 2 2 2 2Acid Flexzone 1 1 1 1 1 1 1 1 7P CBS 1.25 1.25 1.25 1 1 1 1.25 1.25 MBT0.2 0.2 0.2 0.2 Sulfur 1.75 1.75 1.75 1.75 1.5 1.5 1.5 1.5 Total 159.2159.2 159.2 159.2 159.5 159.5 158.75 158.75

[0165] The performance data in the table below show that carbon blackproducts according to the invention are useful in several differentrubber formulations. Abrader Abrader 100% 300% index index ModulusModulus Tensile Hardness Bound Tan Tan 14% 21% Mpa Mpa Mpa Elong. %Shore A rubber % δ 0 C δ 70 C slip slip Example 4.12 19.3 21.9 338 6029.8 0.241 0.155 84 117 109 Comparative 3.70 17.3 23.0 393 62 28.0 0.2800.182 100 100 Example 4.79 — 14.4 233 63 32.4 0.477 0.146 81 175 110Comparative 4.10 — 16.3 282 61 28.6 0.544 0.173 100 100 Example 3.3215.1 24.4 456 55 39.1 0.221 0.142 98 135 111 Comparative 3.48 17.1 27.3468 57 43.6 0.240 0.138 100 100 Example 3.77 15.7 19.0 358 58 33.3 0.2960.156 100 176 112 Comparative 3.39 15.4 23.3 441 58 35.1 0.335 0.175 100100

Example 113 Use of treated Carbon Black in a Rubber Formulation

[0166] This example illustrates the use of a treated carbon black of thepresent invention in a rubber formulation. Rubber compounds wereprepared from the treated carbon black of example 86 and the comparativecarbon black of example 89 by the method described in examples 104-108.The formulations and performance data are shown in the following tables.These results show that the treated carbon black is useful in thisrubber formulation. NS 116 is a chemically modified tin coupled solutionSBR and is available from Nippon Zeon, Japan. Example 113 Comparative NS116 100 100 CB Product 50 Example 86 Control CB Example 89 50 ZnO 3 3Stearic Acid 2 2 FLEXZONE 7P product 1 1 CBS 1.25 1.25 MBT 0.2 0.2Sulfur 1.75 1.75 Total 159.2 159.2 100% 300% Bound Abrader AbraderModulus Modulus Tensile Elong. Hardness rubber Tan Tan index index MpaMpa Mpa % Shore A % δ 0 C δ 70 C 14% strip 21% strip Example 4.46 17.318.3 316 64 28.0 0.787 0.190 72 110 113 Compara- 4.12 16.7 21.2 367 6326.2 0.818 0.219 100 100 tive

Example 114 Use of a Carbon Black Product in a Rubber Formulation

[0167] This example illustrates the use of a carbon black product of thepresent invention in a rubber formulation. Rubber compounds wereprepared from the carbon black product of Example 87 and the comparativecarbon black of Example 89 by the method described in Examples 104-108.The formulations and performance data are shown in the following tables.These results show that the carbon black product is useful in thisrubber formulation. Example 114 Comparative NS 116 100 100 CB ProductExample 87 50 Control CB Example 89 50 ZnO 3 3 Stearic Acid 2 2 FLEXZONE7P product 1 1 CBS 1.25 1.25 MBT 0.2 0.2 Sulfur 1.75 1.75 Total 159.2159.2 Abrader Abrader 100% 300% Bound index index Modulus ModulusTensile Elong. Hardness rubber Tan δ Tan δ 14% 21% Mpa Mpa Mpa % Shore A% 0 C 70 C slip slip Example 5.04 — 16.6 242 60 39.0 0.816 0.145 88 137114 Compara- 4.12 16.7 21.2 367 63 26.2 0.818 0.219 100 100 tive

Examples 115-116 Use of Carbon Black Product in Rubber Formulations

[0168] These examples illustrate the use of a carbon black product ofthe present invention in two rubber formulations that are peroxidecured. Rubber compounds were prepared from the carbon black product ofExample 88 and from an untreated comparative carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 ml/100 g. The method described inExamples 104-108 was used with the recipies below. Example 115Comparative 116 Comparative NS-114 100 100 Duradene 715 100 100 CBProduct 50 50 Example 88 Control CB 50 50 ZnO 3 3 3 3 Stearic Acid 2 2 22 Flexzone 7P 1 1 1 1 Dicumyl peroxide 2 2 2 2 Total 158 158 158 158

[0169] The performance data in the table below show that this carbonblack product is useful in rubber formulations using a peroxide cure.Abrader Abrader 100% 200% index index Modulus Modulus Tensile HardnessBound Tan Tan 14% 21% Mpa Mpa Mpa Elong. % Shore A rubber % δ ° C. 70 °C. slip slip Example 3.66 10.4 23.9 356 61 3.3 0.208 0.119 98 101 115Compara- 2.94 8.1 21.8 398 62 18 0.284 0.156 100 100 tive Example 5.1111.5 13.9 233 67 17.5 0.299 0.152 65 74 116 Compara- 4.07 11.3 20.3 32161 22.1 0.343 0.180 100 100 tive

Example 117 Use of a Carbon Black Product to Color Textiles

[0170] This example illustrates the use of a carbon black of the presentinvention to color textiles. Samples of textiles were placed for thetime indicated below in a stirring dispersion of the carbon blackproduct of Example 16 having attached C₆H₄SO₃— groups at the indicatedconcentrations at 100° C. The pH was adjusted as shown. The samples wereremoved, allowed to drain briefly, and posttreated by placing for about30 seconds in hot water, a hot 1 M solution of NaCl or a hot 0.015 Msolution of Al₂(SO₄)₃. When the pH of the carbon dispersion wasadjusted, the pH of the NaCl and Al₂(SO₄)₃ posttreatment solutions wereadjusted to match. The samples were then washed with water and dried.The L values below show that the textiles were effectively colored withthe carbon black product. Lower L values represent darker materials.Carbon conc. Time Post treatment Textile M pH Min. H2O NaCl Al2(SO4)3Hunter L Cotton 0.1 A 15 X 34.1 Cotton 0.1 A 45 X 33.6 Cotton 0.1 A 45 X30.3 Cotton 0.1 A 45 X 29.1 Cotton 0.01 A 45 X 67.4 Linen 0.1 A 45 X43.2 Linen 0.1 A 45 X 37.3 Linen 0.1 A 45 X 37.8 Wool 0.1 3.5 15 X 22.2Wool 0.1 3.5 45 X 18.6 Wool 0.1 3.5 45 X 20.0 Wool 0.1 3.5 45 X 17.8Wool 0.1 5.5 45 X 28.0 Silk 0.1 5.5 15 X 34.9 Silk 0.1 5.5 45 X 34.9Silk 0.1 5.5 45 X 41.4 Silk 0.1 5.5 45 X 22.2 Polyester 0.1 A 45 X 45.1Nylon 0.1 3.5 15 X 41.6 Nylon 0.1 3.5 45 X 35.3 Nylon 0.1 3.5 45 X 35.4Nylon 0.1 3.5 45 X 27.8 Nylon 0.1 5.5 45 X 34.8

Carbon Black Products Example 118

[0171] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0172] 4-aminophenyl-2-benzothiazolyl disulfide was prepared accordingto the method described in Brzezinska, E.; Ternay, Jr., A. L. J. Org.Chem. 1994, vol. 59, pp. 8239-8244.4-aminophenyl-2-benzothiazolyldisulfide (9.79 g) was dissolved in 300 mL of ethanol at 75° C. andadded to a stirred slurry containing 225 g of carbon black pellets in 1liter of ethanol and 6.37 g of 70% nitric acid. To the resulting slurrywas added a 10 mL solution of NaNO₂ (2.64 g). Gas was evolved. Afterstirring for 48 hours most of the ethanol had evaporated and theresulting carbon black product was collected washed with water and driedat 125° C. to a constant weight.

[0173] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.77% sulfur, compared to 1.12%for the untreated black. Therefore, the carbon black product had 0.07mmol/g of attached -(4-C₆H₄)—S—S-(2-C₇H₅NS) groups.

Example 119

[0174] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0175] 4-aminophenyl-2-benzothiazolyl disulfide (14.1 g) was prepared asin Example 118 and was dissolved in a solution consisting of 10.1 g of37% HCl, 360 mL of water and 560 mL of acetone. The orange solution wasthen added to a stirred slurry of carbon black pellets in 0.8 liters ofwater and 1.2 liters of acetone. A solution of NaNO₂ (3.81 g) in 60 mLof water and 90 mL of acetone was added to the slurry in one portion.Gas was evolved. The slurry was stirred overnight and filtered tocollect the carbon black product. The carbon black product was washedwith water, collected by filtration and dried at 125° C. to a constantweight.

[0176] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.77% sulfur, compared to 1.09%for the untreated black. Therefore, the carbon black product had 0.07mmol/g of attached —(4-C₆H₄)—S—S—(2-C₇H₅NS) groups.

Example 120

[0177] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0178] 4-aminophenyl-4′-hydroxyphenyl disulfide was prepared as follows.4-aminophenyl-2-benzothiazolyl disulfide (14.5 g) was dissolved in 325mL of chloroform yielding an orange solution. Over the course of 30minutes a solution of 4-hydroxythiophenol (6.78 g) in 60 mL ofchloroform was added dropwise. After addition was complete, the reactionmixture was stirred overnight. The chloroform solution was extracted ina separatory funnel with a solution of 5.3 g of 37% HCl diluted in 200mL of water. The aqueous layer was collected, neutralized with 5% NaOH,and extracted with ethyl acetate. The ethyl acetate layer was isolated,dried over MgSO₄ and filtered. Removal of the ethyl acetate gave 10.5 gof 4-aminophenyl-4′-hydroxyphenyl disulfide as a yellow oil.

[0179] To a stirred slurry of 4-aminophenyl-4′-hydroxyphenyl disulfide(8.13 g), prepared as descrbed above, in 300 mL of water was added asolution of 6.99 g of 37% HCl in 75 mL of water. The resulting whitesuspension was added to a slurry of 225 g of carbon black pellets in 1.5liters of water and the mixture stirred for 5 minutes. A solution ofNaNO₂ (2.64 g) in 100 mL of water was added to the slurry. Gas wasevolved. After stirring the slurry overnight, the carbon black productwas isolated by filtration and washed with water. The carbon blackproduct was then dried at 125° C. to constant weight.

[0180] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.67% sulfur, compared to 1.11%for the untreated black. Therefore, the carbon black product had 0.09mmol/g of attached -(4-C₆H₄)—S—S-(4-C₆H₄)—OH groups.

Example 121

[0181] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0182] To a stirred slurry of 237 g of carbon black pellets in 1.4liters of water was added a solution of 4.44 g of 4-aminothiophenol and7.36 g of 37% HCl in 250 mL of water. To the resulting slurry was addeda solution of NaNO₂ (2.78 g) in 75 mL of water. Gas was evolved. Theslurry was stirred for 2.5 hours, filtered, and washed with water. Thecarbon black product was then dried at 125° C. to constant weight.

[0183] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.63% sulfur, compared to 1.11%for the untreated black. Therefore, the carbon black product had 0.15mmol/g of attached —(4-C₆H₄)—SH groups.

Example 122

[0184] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0185] To a stirred slurry of 6-amino-2-mercaptobenzothiazole (6.14 g)in 300 mL of water was added 6.99 g of 37% HCl in 75 mL of water. Theresulting slurry was cooled to 10° C., and a similarly cooled solutionof NaNO₂ (2.64 g) in 50 mL of water was added. The resulting orangeslurry was stirred for 30 seconds then added to a stirred slurry of 225g of carbon black pellets in 1.4 liters of water and 300 g of ice. Gaswas evolved. The slurry was stirred for 2.5 hours and then filtered. Thecarbon black product was then washed with water and dried at 125° C. toa constant weight.

[0186] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.98% sulfur, compared to 1.11%for the untreated black. Therefore, the carbon black product had 0.135mmol/g of attached -6-(2-C₇H₄NS)—SH groups.

Example 123

[0187] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0188] Bis[2-(4-aminophenyl)ethyl]disulfide was prepared as follows. Toa refluxing solution of 4-nitrophenylethylbromide (23 g) in a mixture of280 mL of methanol and 70 mL of water was added a solution ofNa₂S₂O₃.5H₂O (31 g) in 75 mL of water. A further 60 mL of water was thenadded to the reaction mixture. Refluxing conditions were continued for 5hours. The resulting pale yellow solution was allowed to cool to roomtemperature. Methanol was removed from the solution on a rotaryevaporator leaving a white crystalline aqueous slurry. Addition of 300mL of water to the slurry yielded a slightly cloudy solution. To thisaqueous solution of sodium 4-nitrophenylethyl-thiosulfate was added asolution of Na₂S·9H₂O (120 g) in 300 mL of water. The reaction mixturerapidly grew cloudy and slightly yellow and, after several minutes ofstirring, a white precipitate formed. This slurry was heated to refluxfor 18 hours then cooled. An orange oil was present which was extractedwith several portions of ethyl acetate. The ethyl acetate extracts werecombined, dried over MgSO₄, and filtered. Removal of the ethyl acetateyielded 12 g of bis[2-(4-aminophenyl)ethyl] disulfide as an orange oil.

[0189] To a stirred slurry of bis[2-(4-aminophenyl)ethyl]disulfide (5.02g), prepared as described above, in 200 mL of water was added a solutionof 6.67 g of 37% HCl in 100 mL of water. After stirring for 20 minutesan orange solution was obtained and was added to a stirred slurry ofcarbon black pellets in 1 liter of water. To the resulting slurry wasadded a solution of NaNO₂ (2.46 g) in 100 mL of water. Gas was evolved.After stirring the slurry overnight, the carbon black product wasfiltered, washed with water, and dried at 125° C. to a constant weight.

[0190] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.81% sulfur, compared to 1.11%for the untreated black. Therefore, the carbon black product had 0.11mmol/g of attached —(4-C₆H₄)—CH₂CH₂—S—S—CH₂CH₂-(4-C₆H₄)— groups.

Example 124

[0191] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0192] Bis[2-(4-aminophenyl)ethyl]trisulfide was prepared as follows. Toa slurry of iron powder (28.4 g) in 300 mL of water at 100° C. in a 500mL Erlenmeyer flask was added 1.42 g of FeSO₄.7H₂O.4-nitrophenylethylthiosulfate (29 g), prepared according to theprocedure outlined in Example 123, was added to the iron slurry in 1gram portions over the course of 5 minutes while maintaining atemperature of 96-98° C. During the addition, the flask was manuallyshaken to ensure good mixing. After the addition of4-nitrophenylethylthiosulfate was complete, a further 9.5 g of Fe wasadded and heating continued for 5 minutes. Once the flask had cooled toroom temperature, several drops of conc. NH₄₀H were added to adjust thepH of the reaction mixture from 5 to 9.5. The mixture was then filteredand the iron and iron salts washed with two 50 mL portions of water. Theyellow filtrate was acidified with 37% HCl to a pH of 1. At about a pHof 5, a white precipitate began to form. After cooling the acidifiedfiltrate at 5° C. overnight, the solid was collected by filtration,washed with water then acetone, and air dried. Approximately 14.3 g ofS-(4-aminophenylethyl)thiosulfuric acid was isolated.

[0193] To a slurry of 16 g S-(4-aminophenylethyl)thiosulfuric acid in500 mL of water was added solid NaHCO₃ to adjust to pH to 8. As the pHwas raised the solid dissolved yielding a solution of sodiumS-(4-aminophenylethyl)thiosulfate. To this was added a solution ofNa₂S.9H₂O (12.3 g) in 150 mL of water dropwise over the course of 30minutes with the concomitant formation of a precipitate. After theaddition was complete, the reaction mixture was stirred for 15 minutesand then extracted twice in a separatory funnel with first 200 mL then100 mL of ethyl acetate. The ethyl acetate extracts were combined anddried over MgSO₄. The ethyl acetate was evaporated leaving a yellowsolid. Final isolated yield of bis[2-(4-aminophenyl)ethyl]trisulfide was11.3 g.

[0194] To a stirred slurry of bis[2-(4-aminophenyl)ethyl]trisulfide(11.3 g), prepared as described above, in 300 mL of water was added asolution 13.7 g of 37% HCl diluted in 100 mL of water. After stirringfor 20 minutes, an additional 200 mL of water was added and the mixturegently heated to 45° C. and stirred for 15 minutes to obtain a solution.The resulting solution was cooled to room temperature and added to astirred slurry of carbon black pellets (225 g) in 1.2 liters of water.Next, a solution of NaNO₂ (5.04 g) in 100 mL of water was added to thecarbon black slurry. Gas was evolved. The reaction mixture was stirredovernight and the carbon black product isolated by filtration, washedwith water, and dried at 125° C. to a constant weight.

[0195] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 2.09% sulfur, compared to 1.11%for the untreated black. Therefore, the carbon black product had 0.10mmol/g of attached -(4-C₆H₄)—CH₂CH₂—S—S—S—CH₂CH₂-(4-C₆H₄)— groups.

Example 125

[0196] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0197] To a stirred slurry of bis(2-aminophenyl) disulfide in 500 mL ofwater was added a solution of 13.6 g of 37% HCl in 80 mL of water. Theresulting slurry was heated to 65° C. yielding a gold solution with abrown solid. After filtering the hot solution to remove the solid, thesolution was then added with stirring to a room temperature slurry ofcarbon black pellets (225 g) in 1.2 liters of water. A solution of NaNO₂(5.04 g) in 90 mL of water was then added to the carbon black slurryover the course of a minute. Gas was evolved. The mixture was stirredfor 2 hours, filtered and washed with water, and dried at 125° C. to aconstant weight.

[0198] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.44% sulfur, compared to 1.12%for the untreated black. Therefore, the carbon black product had 0.05mmol/g of attached -(2-C₆H₄)—S—S-(2-C₆H₄)— groups.

Example 126

[0199] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0200] Bis(3-aminophenyl) disulfide was prepared as follows frombis(3-nitrophenyl) disulfide following a procedure similar to the onedescribed by W. A. Sheppard in Organic Syntheses, Coll. Vol. 5, p. 843.To 13.7 g of solid 3-nitrobenzenesulfonyl chloride was added 46 mL of47% hydriodic acid (HI) yielding a dark brown mixture. The mixture wasrefluxed for 2.5 hours. During the course of the reaction, the iodineby-product sublimed into the water condenser and was removed atappropriate intervals to prevent clogging of the condenser. When thereaction mixture had cooled, NaHSO₃ was added to neutralize theremaining iodine. The resulting slurry was filtered to collect thesolid, and the solid was washed with 200 mL of water. The solid was thenextracted on the filter with 300 mL of acetone yielding an orangesolution. Removal of the acetone gave 8.4 g of bis(3-nitrophenyl)disulfide as a orange solid.

[0201] To a stirred slurry bis(3-nitrophenyl) disulfide (8.4 g) in 100mL of water was added a solution of Na₂S.9H₂O (20.4 g) in 100 mL ofwater. The reaction mixture was heated to reflux at which point a darkred solution was obtained. After refluxing for 18 hours, an additional 5g of Na₂S.9H₂O was added to the reaction mixture and heating continuedfor 2 hours. To the cooled reaction mixture was added 3.5 g of 30% H₂O₂in a dropwise manner. The white precipitate which formed was extractedtwice with 100 mL of ethyl acetate. The ethyl acetate extracts werecombined and dried over MgSO₄. Removal of the ethyl acetate gave 5.9 gof bis(3-aminophenyl) disulfide.

[0202] To a stirred slurry of of bis(3-aminophenyl) disulfide (10.2 g),prepared as described above, in 0.7 liters of water was added a solutionof 18 g of 37% HCl in 50 mL of water. This solution was cooled to 10°C., and a similarly cooled solution of NaNO₂ (6.1 g) in 75 mL of waterthen added. This mixture was then added to a stirred slurry of carbonblack pellets (225 g) in 1.8 liters of water. Gas was evolved. Afterstirring for 2 hours, the carbon black product was isolated byfiltration, washed with water and dried at 115° C. to a constant weight.

[0203] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.71% sulfur, compared to 1.11%for the untreated black. Therefore, the carbon black product had 0.09mmol/g of attached -(3-C₆H₄)—S—S-(3-C₆H₄)— groups.

Example 127

[0204] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0205] 6-amino-1,2,3-benzothiadiazole was prepared according to themethod described in Ward, E. R.; Poesche, W. H.; Higgins, D.; and Heard,D. D. J. Chem. Soc. 1962, pp. 2374-2379. A solution of 3.5 g HCl in 50mL water was added to solid 6-amino-1,2,3-benzothiadiazole (2.38 g), andthe resulting solution cooled to 10° C. Next, a cold solution of NaNO₂(1.1 g) in 50 mL was added, and this mixture was then added to a stirredslurry of carbon black pellets (105 g) in 500 mL of water and 100 g ofice. Gas was evolved. After stirring the mixture for 3 hours, the carbonblack product was collected by filtration, washed with water andisopropanol, and air dried to a constant weight.

[0206] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.50% sulfur, compared to 1.06%for the untreated black. Therefore, the carbon black product had 0.14mmol/g of attached -6-(C₇H₅N₂S) groups.

Example 128

[0207] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0208] N-morpholino-(6-aminobenzothiazole)-2-sulfenamide was prepared asfollows. A solution of NaI₃ was prepared by adding 12 (35.5 g) to anaqueous solution consisting of NaI (47 g) dissolved in 150 mL of water.Next, 6-amino-2-mercaptobenzothiazole (6.5 g) was added to a solutionconsisting of NaOH (2.84 g) in 50 mL of water. After stirring for 15minutes, a red-brown solution was obtained to which morpholine (9.28 g)was added. To this mixture was added the previously prepared NaI₃solution. A brown precipitate formed and the slurry was stirred for 4hours. The solid was isolated by filtration and air dried. The solid wasslurried in 75 mL of ethanol and 3.34 g of morpholine. To this slurrywas added dropwise a solution of 3.24 g of 12 in 60 mL of ethanol overthe course of 20 minutes. After stirring the mixture at room temperatureovernight, the ethanol was removed on a rotary evaporator and theresidue washed with an aqueous solution of NaI to remove unreactediodine. The product was collected by filtration, washed with 250 mL ofwater, and then dried in a vacuum oven at 60° C. for 6 hours. 9.2 g ofN-morpholino-(6-aminobenzothiazole)-2-sulfenamide was isolated in 80%purity.

[0209] To a stirred slurry containing carbon black pellets (175 g),N-morpholino-(6-aminobenzothiazole)-2-sulfenamide (7.01 g) and NaNO₂(1.96 g) in 1 liter of water was added a solution consisting of 5.43 gof 37% HCl diluted in 75 mL of water. Gas was evolved. After stirringthe slurry for 48 hours, the carbon black product was filtered, washedwith water, and dried at 100° C. to a constant weight.

[0210] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.62% sulfur, compared to 1.12%for the untreated black. Therefore, the carbon black product had 0.08mmol/g of attached -6-(2-C₇H₄NS)—S—NRR′ groups, where RR′ is—CH₂CH₂OCH₂CH₂—.

Example 129

[0211] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0212] Bis(4-aminophenyl) tetrasulfide was prepared as follows. Under anitrogen atmosphere, a solution of 9.74 g of 4-aminothiophenol in 150 mLof anydrous tetrahydrofuran (THF) was prepared. The solution was thencooled in a dry ice/ethanol bath. Butyl lithium was added to the flaskand a thick yellow precipitate formed. Another 125 mL of THF was addedto the flask and the flask warmed in an ice water bath to 5° C. Sulfurmonochloride, S₂Cl₂, (2.80 mL) was added to the slurry over the courseof 5 seconds resulting in a red solution. After standing overnight at−15° C., the reaction mixture was warmed to room temperature and the THFremoved using a rotary evaporator. The orange oil was redissolved inCH₂Cl₂, filtered through Celite to remove insoluble LiCl and dried overMgSO₄. After filtering the solution to remove the MgSO₄, CH₂Cl₂ wasremoved yielding 11.4 g of bis(4-aminophenyl) tetrasulfide as an orangeoil.

[0213] A solution of 13 g of 37% HCl in 75 mL of water was added to aslurry of bis(4-aminophenyl) tetrasulfide (10 g), prepared as describedabove, in 200 mL of water, and the resulting mixture was stirred for 15minutes. The orange-red suspension was cooled to 10° C., and a similarlycooled solution of NaNO₂ (4.8 g) in 60 mL of water was added over thecourse of 1-2 minutes. The resulting orange-yellow slurry was combinedwith a stirred slurry of carbon black pellets (213 g) in 1 liter ofwater and 200 g of ice. Gas was evolved. After stirring the mixtureovernight, the carbon black product was isolated by filtration, washedwith water, and dried at 120° C. to a constant weight.

[0214] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 2.40% sulfur, compared to 1.23%for the untreated black. Therefore, the carbon black product had 0.09mmol/g of attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 130

[0215] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0216] Bis(4-aminophenyl) tetrasulfide was prepared as follows. To astirred slurry of 4-nitrochlorobenzene (59 g) in 600 mL of water wasadded a solution consisting of Na₂S.9H₂O (240 g) dissolved in 200 mL ofwater. The resulting mixture was heated to reflux over the course of 45minutes and continued for 17 hours. At the end of 17 hours a smallamount of oil was present in the flask. After allowing the reactionmixture to cool to room temperature, the aqueous solution was decantedfrom the oil and then filtered. Next, elemental sulfur powder (72 g) wasadded to the aqueous filtrate and the resulting slurry heated to reflux.After 22 hours, a large amount of orange oil was present in thereaction. Heat was removed and the reaction mixture cooled to roomtemperature. The orange oil was extracted into 500 mL of ethyl acetate.Once the ethyl acetate solution had been filtered and dried over MgSO₄,the ethyl acetate was removed to give bis(4-aminophenyl) tetrasulfide asan orange oil.

[0217] Bis(4-aminophenyl) tetrasulfide (10.5 g), prepared as describedabove, was stirred in 300 mL of water, and to this was added a solutionof 13.7 g of 37% HCl diluted in 100 mL of water. After stirring 15minutes, an additional 200 mL of water was added. Stirring for another45 minutes yielded a finely divided suspension. The suspension wasfiltered to remove the solid, and the filtrate was combined with astirred slurry of carbon black pellets (225 g) in 1.2 liters of water.Next, a solution of NaNO₂ (5.04 g) in 50 mL of water was added to thecarbon black slurry. Gas was evolved. After stirring the mixtureovernight, the carbon black product was isolated by filtration, washedwith water and dried at 120° C. to a constant weight.

[0218] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 2.36% sulfur, compared to 1.09%for the untreated black. Therefore, the carbon black product had 0.10mmol/g of attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 131

[0219] A carbon black product having attached-(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups was prepared by following the methodof Example 130 and using a suspension of 7.03 g of 4-aminophenyltetrasulfide in 200 mL of water, a solution 9.09 g of 37% HCl in 75 mL,a solution of 3.36 g of NaNO₂ in 100 mL of water, and a slurry 225 g ofthe same carbon black pellets in 1.2 liters of water.

[0220] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.63% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.05mmol/g of attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 132

[0221] A carbon black product having attached-(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups was prepared by following the methodof Example 130 and using a suspension of 5.27 g of 4-aminophenyltetrasulfide in 200 mL of water, a solution 6.82 g of 37% HCl in 75 mL,a solution of 2.52 g of NaNO₂ in 100 mL of water, and a slurry 225 g ofthe same carbon black pellets in 1.2 liters of water.

[0222] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.54% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.03mmol/g of attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 133

[0223] A carbon black product having attached-(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups was prepared by following the methodof Example 130 and using a suspension of 3.22 g of 4-aminophenyltetrasulfide in 200 mL of water, a solution 4.16 g of 37% HCl in 75 mL,a solution of 1.54 g of NaNO₂ in 100 mL of water, and a slurry 206 g ofthe same carbon black pellets in 1.2 liters of water.

[0224] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.26% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.02mmol/g of attached -(4-C₆H₄)—S—S—S—S-(4-C₆H₄)— groups.

Example 134

[0225] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0226] Liquid 4-aminostyrene (4.02 g) was added to a dilute aqueous acidsolution previously prepared by adding 7.33 g of 37% HCl to 150 mL ofwater. After stirring the mixture for 5 minutes, a yellow solution wasobtained and added to stirred slurry of carbon black pellets (225 g) in1.2 liters of water. Addition of a solution of NaNO₂ (2.94 g) dissolvedin 50 mL of water resulted in the formation of gas. After stirring themixture for 3 hours, the carbon black product was isolated byfiltration, washed with water, and dried at 125° C. to a constantweight.

[0227] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 0.46% hydrogen, compared to 0.37%for the untreated black. Therefore, the carbon black product had 0.06mmol/g of attached -(4-C₆H₄)—CH═CH₂ groups.

Example 135

[0228] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0229] S-(4-aminophenyl)thiosulfuric acid (6.60 g) was prepared by themethod described in Tanaka et al, Chem. Pharm. Bull. 1974, vol. 22, p.2725, and was dissolved in 600 mL of water containing 3.50 g of 37% HCl.This solution was added to a stirred slurry of carbon black pellets (215g) in 1.2 liters of water. Next, an aqueous solution of NaNO₂ (2.52 g)in 30 mL of water was added to the slurry. Gas was evolved. Afterstirring the mixture for 2 hours then standing overnight, the carbonblack product was isolated by filtration, washed with water, and driedat 125° C. to a constant weight.

[0230] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.58% sulfur, compared to 1.23%for the untreated black. Therefore, the carbon black product had 0.05mmol/g of attached -(4-C₆H₄)—S—SO₃H groups.

Example 136

[0231] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0232] Bis[4-(4′-aminobenzenesulfonamido)phenyl] disulfide was preparedas follows. To N-acetylsulfanilyl chloride (20.0 g) stirring in acetone(500 mL) at room temperature was added 4-aminophenyl disulfide (10.12 g)followed by pyridine (7.09 g). The cloudy yellow-orange reaction mixturewas allowed to stir for 20 hours, during which time a clear, goldenyellow solution formed. 7.5 mL of 37% HCl was added to 45 mL of water,and this acid solution was added to the reaction mixture. The acetonewas removed, and the remaining mixture was diluted with 100 mL of waterand extracted with ethyl acetate (2×200 mL). The combined ethyl acetateextracts were washed with water (5×100 mL), washed with a saturatedbrine solution (1×100 mL), dried over Na₂SO₄, and filtered. Removal ofthe ethyl acetate yielded 29.37 g of crude product as a tan foam. Thismaterial was added to a flask containing THF (150 mL), and 2N HCl (150mL) was added. The resulting slurry was heated to reflux. After 24 hoursat reflux, 48 mL of 2N HCl were added, and the reaction was continued atreflux for 22 hours. The clear orange solution was allowed to cool toroom temperature and carefully made basic with solid NaHCO₃, and theresulting mixture extracted with ethyl acetate (3×200 mL). The combinedethyl acetate extracts were washed with water (4×200 mL) until neutral,dried over Na₂SO₄, and filtered. Removal of the ethyl acetate yielded20.2 g of the desired product as a yellow solid.

[0233] Bis[4-(4′-aminobenzenesulfonamido)phenyl]disulfide (18.83 g),prepared as described above, was dissolved in a mixture of 500 mL ofwater, 632.4 g of acetone, and 13.65 g of 37% HCl. This yellow solutionwas cooled in an ice water bath, and NaNO₂ (13.65 g) was added, yieldinga deep red solution containing an orange precipitate. This mixture wasadded in one portion to a rapidly stirring slurry of carbon blackpellets (225 g) in 1/1 acetone/water (1.5 liters total). Gas wasevolved. The slurry was stirred overnight and filtered to collect thecarbon black product. The carbon black product was washed with water,collected by filtration, and dried at 125° C. to a constant weight.

[0234] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 2.21% sulfur, compared to 1.14%for the untreated black. Therefore, the carbon black product had 0.084mmol/g of attached -(4-C₆H₄)—SO₂NH-(4-C₆H₄)—S—S-(4-C₆H₄)—NHSO₂-(4-C₆H₄)—groups.

Example 137

[0235] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0236] p-Phenylenediamine (4.87 g) was dissolved in 250 mL of watercontaining 9.11 g of 37% HCl. This was cooled in an ice bath, and asolution of 3.36 g NaNO₂ dissolved in 125 mL of water was added. Theresulting blue-green solution was added in one portion to a rapidlystirring slurry of carbon black pellets (225 g) in 2 liters of watercontaining 280 g of ice. The slurry was stirred overnight and filteredto collect the carbon black product. This product was washed with water,collected by filtration, and dried at 125° C. to a constant weight.

Example 138

[0237] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.p-Phenylenediamine (2.43 g) was dissolved in 250 mL of water containing9.11 g of 37% HCl. This was cooled in an ice bath, and a solution of3.36 g NaNO₂ dissolved in 125 mL of water was added. This blue-greensolution was added in one portion to a rapidly stirring slurry of carbonblack pellets (225 g) in 2 liters of water containing 280 g of ice. Theslurry was stirred overnight and filtered to collect the carbon blackproduct. This product was washed with water, collected by filtration,and dried at 125° C. to a constant weight.

Example 139

[0238] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0239] 2,2′-bis(6-aminobenzothiazolyl) disulfide was prepared asfollows. 6-Amino-2-mercaptobenzothiazole (15.0 g) was added to 500 mL ofwater. To this slurry was added a solution of NaOH (3.3 g) dissolved in1 liter of water, and the mixture stirred for 1 hour at room temperatureuntil most of the thiol was dissolved. A solution containing NaI (24.73g) and 12 (10.47 g) in 750 mL of water was added to the thiolatesolution gradually over 1.5 hours with vigorous stirring. During theaddition, a thick slurry containing a yellowish solid formed. After theaddition and continued stirring for an additional 45 minutes, the solidwas isolated by filtration. 2,2′-bis(6-aminobenzothiazolyl)-disulfide(12.23 g), prepared as described above, was added to 600 mL of watercontaining 13.66 g of 37% HCl. This yellow slurry was cooled in an icebath, and a solution of 5.04 g NaNO2 dissolved in 50 mL of water wasadded. The resulting dark brown mixture was added in one portion to arapidly stirring slurry of carbon black pellets (225 g) in 2 liters ofwater containing 280 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. The product was washedwith water and isopropanol, collected by filtration, and dried at 125°C. to a constant weight.

[0240] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.69% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.054mmol/g of attached -6-(2-C₇H₄NS)—S—S-2-(6-C₇H₄NS)— groups.

Example 140

[0241] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0242] 4-aminophenyl4-aminobenzyl sulfide was prepared as follows. Asolution of NaOH (7.1 g) in water (200 mL) was added to a mixture of4-aminothiophenol (19.8 g) in 190 mL of water. The mixture was stirreduntil most of the thiophenol was dissolved. To this mixture was added4-nitrobenzyl chloride (25.8 g) in portions with good stirring. Theresulting yellow solution was then stirred at reflux for 1.5 hours,during which time a thick red oil separated. At the end of the reaction,the mixture was allowed to cool to room temperature, and the red oilseparated as a waxy solid. The solid was extracted with ethyl acetate(400 mL followed by 100 mL), and the combined ethyl acetate extractswere dried over Na₂SO₄ and filtered. Removal of the ethyl acetateyielded 38.65 g of 4-aminophenyl-4-nitrobenzyl sulfide.

[0243] All of the above product was dissolved in a mixture of ethanol(235 mL) and water (780 mL). To this solution was added 37% HCl (27.83g) and iron powder (49.78 g), and the slurry stirred at reflux for 3hours. After cooling to room temperature, 200 mL of water were added,and the mixture was extracted with ethyl acetate (600 mL followed by 200mL). The combined ethyl acetate extracts were dried over Na₂SO₄ andfiltered. Removal of the ethyl acetate yielded 31.53 g of the desiredproduct.

[0244] 4-aminophenyl-4-aminobenzyl sulfide (7.77 g), prepared asdescribed above, was added to 250 mL of water containing 13.7 g of 37%HCl. The resulting solution was cooled in an ice bath and a solution of5.04 g NaNO₂ dissolved in 125 mL of water added. The resulting mixturewas added in one portion to a rapidly stirring slurry of carbon blackpellets (225 g) in 2 liters of water containing 280 g of ice. The slurrywas stirred overnight and filtered to collect the carbon black product.This product was collected by filtration, washed with water then withethanol, collected by filtration, and dried at 125° C. to a constantweight.

[0245] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.38% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.12mmol/g of attached -(4-C₆H₄)—S—CH₂-(4-C₆H₄)— groups.

Example 141

[0246] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0247] Bis(4-aminophenyl)thiosulfonate was prepared following a modifiedprocedure to the one described in Leitch, L.; Baker, B.; Brickman, L.Can. J. Res. Sect. B 1945, 23, 139. To a well-stirred mixture ofthiourea (11.4 g) in acetone (175 mL) was added pyridine (16.85 mL)followed by N-acetylsulfanilyl chloride (35.05 g). A yellow colordeveloped. This mixture was heated to reflux and stirred under theseconditions for 80 minutes. The reaction was then allowed to cool to roomtemperature, and a fluffy solid precipitated. After removing theacetone, 500 mL of hot water were added. A pale yellow precipitateformed, which was isolated by filtration, yielding 22.7 g ofbis(4-acetamidophenyl)thiosulfonate.

[0248] The desired final product was obtained following a modificationto the procedure described in Bere, C.; Smiles, S. J. Chem. Soc. 1924,2359. All of the bis-(4-acetamidophenyl)thiosulfanate prepared above(22.7 g) was dissolved in 250 mL of THF, and 250 mL of 2N HCl was added.The mixture was heated to reflux and stirred for 5 hours. After allowingthe reaction to cool to room temperature, most of the THF was removedand solid NaHCO₃ added carefully until no further gas evolution wasseen. An orange precipitate formed, which was isolated by filtration,yielding the desired bis(4-aminophenyl)thiosulfonate (10.3 g).

[0249] Bis(4-aminophenyl)thiosulfonate (9.46 g), prepared as describedabove, was added to 250 mL of water containing 13.65 g of 37% HCl, andthe cloudy yellow mixture cooled in an ice bath. To this was added asolution of 5.04 g NaNO₂ dissolved in 125 mL of water. A yellowcolloidal suspension formed. The resulting mixture was added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in2 liters of water containing 280 g of ice. The slurry was stirredovernight and filtered to collect the carbon black product. The productwas washed with water and collected by filtration. This was then washedwith ethanol, collected by filtration, and dried at 125° C. to aconstant weight.

[0250] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.85% sulfur, compared to 1.30%for the untreated black. Therefore, the carbon black product had 0.086mmol/g of attached -(4-C₆H₄)—SO₂—S-(4-C₆H₄)— groups.

Example 142

[0251] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0252] Bis(4-aminobenzyl) sulfide was prepared as follows. A solution of4-nitrobenzyl chloride (55.0 g) in 500 mL of THF was added slowly, withgood stirring, to a solution of Na₂S.9H₂O (43.2 g) in 1 liter of water.The mixture was stirred at room temperature for 18 hours. Removal of theTHF and filtration yielded 46.8 g of bis(4-nitrobenzyl) sulfide.

[0253] All of this material was dissolved in 530 mL of ethanol. Water(1.1 liters) was added followed by 530 mL of 2N HCl and 69.1 g of ironpowder. While stirring vigorously, the mixture was heated at reflux for3 hours. After cooling to room temperature, 800 mL of water were added,and the reaction mixture was extracted with 1900 mL of ethyl acetate inseveral portions. The combined ethyl acetate extracts were dried overNa₂SO₄, and filtered. Removal of the ethyl acetate yielded 28.9 g of thedesired bis(4-aminobenzyl) sulfide.

[0254] Bis(4-aminobenzyl) sulfide (12.8 g), prepared as described above,was added to 700 mL of water containing 21.3 g of 37% HC 1. Theresulting solution was stirred for 2 hours and then cooled in an icebath. A solution of 7.84 g NaNO₂ dissolved in 75 mL of water was added.The resulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (350 g) in 2.5 liters ofwater containing 280 g of ice. The slurry was stirred overnight and thenfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

[0255] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.34% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.11mmol/g of attached -(4-C₆H₄)—CH₂—S—CH₂-(4-C₆H₄)— groups.

Example 143

[0256] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0257] Bis(4-aminobenzyl) sulfide (10.99 g), prepared as described forExample 142 ove, was added to 700 mL of water containing 18.2 g of 37%HCl. After stirring for 2 hours, the solution was cooled in an ice bath.A solution of 6.72 g NaNO₂ dissolved in 75 mL of water was added. Theresulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (225 g) in 2 liters ofwater containing 280 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

[0258] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.40% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.125mmol/g of attached -(4-C₆H₄)—CH₂—S—CH₂-(4-C₆H₄)— groups.

Example 144

[0259] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0260] Bis(3-aminobenzyl) sulfide was prepared as follows. A solution of3-nitrobenzyl chloride (55.0 g) in 500 mL of THF was added to a solutionof Na₂S.9H₂O (43.2 g) in 1 liter of water slowly with good stirring.This mixture was stirred at room temperature for 18 hours. Removal ofthe THF and filtration yielded 45.8 g of bis(3-nitrobenzyl) sulfide.

[0261] All of this material was dissolved in 530 mL of ethanol. 11.1liters of water was added followed by 140 mL of 2N HCl and 67.64 g ofiron powder. While stirring vigorously, the mixture was heated to refluxfor 4.5 hours. More iron powder (15.0 g) was added, and the reaction wascontinued at reflux for an additional 1 hour. After cooling to roomtemperature, the reaction mixture was extracted several times with ethylacetate. The combined ethyl acetate extracts were dried over Na₂SO₄, andfiltered. Removal of the ethyl acetate yielded 33.1 g of the desiredbis(3-aminobenzyl) sulfide.

[0262] Bis(3-aminobenzyl) sulfide (10.99 g), prepared as describedabove, was added to 400 mL of water containing 18.2 g of 37% HCl. Afterstirring for 2 hours, the solution was cooled in an ice bath. A solutionof 6.72 g NaNO₂ dissolved in 75 mL of water was added. The resultingbrown colloidal suspension was added in one portion to a rapidlystirring slurry of carbon black pellets (225 g) in 2 liters of watercontaining 280 g of ice. The slurry was stirred overnight and filteredto collect the carbon black product. The product was washed with ethanolthen with water, collected by filtration, and dried at 125° C. to aconstant weight.

[0263] A sample of the carbon black product which had been extractedwith THF overnight and dired contained 1.50% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.09mmol/g of attached -(3-C₆H₄)—CH₂—S—CH₂-(3-C₆H₄)— groups.

Example 145

[0264] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0265] Bis(3-aminobenzyl) sulfide (16.48 g), prepared as described forExample 144 above, was added to 500 mL of water containing 27.32 g of37% HC 1. After stirring for 2 hours, the solution was cooled in an icebath. A solution of 10.1 g NaNO₂ dissolved in 75 mL of water was added.The resulting brown colloidal suspension was added in one portion to arapidly stirring slurry of carbon black pellets (450 g) in 3 liters ofwater containing 300 g of ice. The slurry was stirred overnight andfiltered to collect the carbon black product. This product was washedwith ethanol then with water, collected by filtration, and dried at 125°C. to a constant weight.

[0266] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.30% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.094mmol/g of attached -(3-C₆H₄)—CH₂—S—CH₂-(3-C₆H₄)— groups.

Example 146

[0267] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0268] Bis(4-aminobenzyl) disulfide was prepared as follows. A mixtureof 4-nitrobenzyl chloride (40.0 g) in 933 mL of methanol and 233 mL orwater was heated until a solution formed. To this was added slowly, withgood stirring, a solution of Na₂S₂O₃.5H₂O (72.34 g) in 233 mL of water.This mixture was then stirred at reflux for 4 hours. After cooling toroom temperature, most of the methanol was removed, and to the aqueoussolution (approximately 300 mL) was added a solution of Na₂CO₃ in 600 mLof water. This was stirred at room temperature for 18 hours, duringwhich time a cream colored opaque mixture formed. The precipitate wasisolated by filtration and washed with water yielding 37.1 g ofbis(4-nitrobenzyl) disulfide.

[0269] Bis(4-nitrobenzyl) disulfide (10.0 g) was dissolved in 1.5 litersof ethanol (heating to approximately 73o followed by filtration wasneeded in order to obtain a clear solution). To this heated solution wasadded 0.5 liters of water, 30 mL of 2N HCl, and 16.4 g of iron powder.The temperature was then allowed to drop to approximately 45°, and thereaction was continued at this temperature for 8 hours. The reactionmixture was then heated to reflux and allowed to continue for 3.5 hours.After cooling to room temperature, the mixture was then extractedseveral times with ethyl acetate. The combined ethyl acetate extractswere dried over Na₂SO₄, and filtered. Removal of the ethyl acetateyielded 4.69 g of the desired bis(4-aminobenzyl) disulfide.

[0270] Bis(4-aminobenzyl) disulfide (9.32 g), prepared as describedabove, was added to 250 mL of water containing 13.66 g of 37% HCl. Afterstirring for 2 hours, the solution was cooled in an ice bath. A solutionof 5.04 g NaNO₂ dissolved in 125 mL of water was added. This mixture wasadded in one portion to a rapidly stirring slurry of carbon blackpellets (225 g) in 2 liters of water containing 280 g of ice. The slurrywas stirred overnight and filtered to collect the carbon black product.The product was washed with ethanol then with water, collected byfiltration, and dried at 125° C. to a constant weight.

[0271] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.55% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.086mmol/g of attached -(4-C₆H₄)—CH₂—S—S—CH₂-(4-C₆H₄)— groups.

Example 147

[0272] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/00 g was used.

[0273] Bis(3-aminobenzyl) disulfide was prepared as follows. A solutionof Na₂S₂O₃.5H₂O (72.34 g) in 233 mL of water was added slowly, with goodstirring, to a solution of 3-nitrobenzyl chloride (40.0 g) in 933 mL ofmethanol and 233 mL of water. The resulting mixture was then stirred atreflux for 4 hours. After cooling to room temperature, most of themethanol was removed, and the aqueous layer was extracted with ethylacetate. Removal of the water from the aqueous layer yielded 69.04 g ofthe sodium salt of 3-nitrobenzyl thiosulfate.

[0274] A solution of Na₂CO₃ (124.83 g) in 1 liter of water was graduallyadded to a solution of the sodium salt of 3-nitrobenzyl thiosulfate(39.21 g) in 800 mL of water with good stirring. After stirring at roomtemperature for 18 hours, a cream colored opaque mixture formed. Theprecipitate was isolated by filtration and washed with water yielding16.8 g of bis(3-nitrobenzyl) disulfide.

[0275] Bis(3-nitrobenzyl) disulfide (7.5 g) was dissolved in 1.5 litersof ethanol (this was heated and then filtered while warm in order toobtain a clear solution). To this heated solution was added 750 mL ofwater, 22.5 mL of 2N HCl, and 12.3 g of iron powder. The reaction wasthen further heated to just below the reflux temperature, and heatingwas continued for 5 hours. After cooling to room temperature, 400 mL ofwater was added, and the mixture was then extracted several times withethyl acetate. The combined ethyl acetate extracts were dried overNa₂SO₄, and filtered. Removal of the ethyl acetate yielded 5.15 g of thedesired bis(3-aminobenzyl) disulfide.

[0276] Bis(3-aminobenzyl) disulfide (9.99 g), prepared as describedabove, was added to 250 mL of water containing 14.6 g of 37% HC 1. Afterstirring for 2 hours, the solution was cooled in an ice bath. A solutionof 5.4 g NaNO₂ dissolved in 125 mL of water was added. This mixture wasadded in one portion to a rapidly stirring slurry of carbon blackpellets (241 g) in 2 liters of water containing 280 g of ice. The slurrywas stirred overnight and filtered to collect the carbon black product.This product washed with ethanol then with water, collected byfiltration, and dried at 125° C. to a constant weight.

[0277] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.62% sulfur, compared to 1.00%for the untreated black. Therefore, the carbon black product had 0.097mmol/g of attached -(3-C₆H₄)—CH₂—S—S—CH₂-(3-C₆H₄)— groups.

Example 148

[0278] This example further illustrates the in situ method ofpreparation of a carbon black product of the present invention. A carbonblack with an iodine number of 120 mg/g and a DBPA of 125 mL/100 g wasused.

[0279] N-morpholino-(4-aminophenyl)sulfenamide was prepared as follows.A solution of 12 (14.2 g) in ethanol (300 mL) was added to awell-stirred solution containing 4-diaminophenyl disulfide (13.9 g) andmorpholine (24.4 g) in ethanol (300 mL). The reaction mixture wasstirred at room temperature for 3 hours. Removal of the ethanol gave athick, nearly black oil. It was redissolved in 750 mL of ethyl acetateand washed several times with water. The ethyl acetate layer was driedover Na₂SO₄, and filtered. Removal of the ethyl acetate yielded 19.6 gof the desired N-morpholino-(4-aminophenyl)sulfenamide.

[0280] N-morpholino-(4-aminophenyl)sulfenamide (9.46 g), prepared asdescribed above, was added to a well-stirred mixture of carbon black(225 g), ice (280 g), and water (2 liters). To this was added a solutionof 3.36 g NaNO2 dissolved in 75 mL of water followed by addition of asolution of 37% HCl (4.66 g) in 75 mL of water. The slurry was stirredfor 5 hours, filtered to collect the carbon black product, and dried at125° C. to a constant weight.

[0281] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.26% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.02mmol/g of attached -(4-C₆H₄)—S—NRR′ groups where RR′ is —CH₂CH₂OCH₂CH₂—.

Example 149

[0282] This example further illustrates the in situ method ofpreparation of a carbon black product of the present invention. A carbonblack with an iodine number of 120 mg/g and a DBPA of 125 mL/100 g wasused.

[0283] N-morpholino-(4-aminophenyl)sulfenamide (9.46 g), prepared asdescribed for Example 148 above, was added to a well-stirred mixture ofcarbon black (225 g), ice (280 g), and water (2 liters). To this wasadded a solution of 3.36 g NaNO₂ dissolved in 75 mL of water followed byaddition of a solution of 37% HCl (9.32 g) in 75 mL of water. The slurrywas stirred for 5 hours, filtered to collect the carbon black product,and dried at 125° C. to a constant weight.

[0284] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.34% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.04mmol/g of attached -(4-C₆H₄)—S—NRR′ groups where RR′ is —CH₂CH₂OCH₂CH₂—.

Example 150

[0285] This example further illustrates the method of preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0286] Bis[2-(4-aminobenzenesulfonamido)ethyl] disulfide was prepared asfollows. To a well-stirred mixture of N-acetylsulfanilyl chloride (1.26g) in 50 mL of CH₂Cl₂ in an ice bath was added triethylamine (559 mg)followed by cystamine (2,2′-diaminoethyl disulfide, 400 mg). The icebath was removed, and the reaction was stirred for 18 hours at roomtemperature. Removal of the CH₂Cl₂ gave a brownish-yellow solid, whichwas stirred vigorously in 50 mL of water for 3 hours and filtered togive 1.24 g of bis[2-(4-acetamidobenzenesulfonamido)ethyl] disulfide.

[0287] A sample of bis[2-(4-acetamidobenzenesulfonamido)ethyl] disulfide(1.00 g) was heated to reflux in a mixture of 40 mL of ethanol and 40 mLof 2 N HCl, and stirred at this temperature for 3 hours. After coolingto room temperature, 200 mL of water were added and the mixture madebasic by carefully adding solid NaHCO₃. A white precipitate formed whichwas isolated by extraction of the basic aqueous layer with ethyl acetate(2×150 mL). The combined ethyl acetate extracts were dried over Na₂SO₄and filtered. Removal of the ethyl acetate yielded 735 mg of the desiredbis[2-(4-aminobenzenesulfonamido)ethyl] disulfide.

[0288] Bis[2-(4-aminobenzenesulfonamido)ethyl] disulfide (15.6 g),prepared as described above, was added to 275 mL of water containing13.6 g of 37% HCl and the mixture cooled in an ice bath. Next, asolution of 5.04 g NaNO₂ dissolved in 60 mL of water was added to themixture. The resulting yellow slurry was added in one portion to arapidly stirring slurry of carbon black pellets (225 g) in 1.2 liters ofwater. The slurry was stirred overnight and filtered to collect thecarbon black product. This product was washed with water, collected byfiltration, and dried at 100° C. to a constant weight.

[0289] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 2.06% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.07mmol/g of attached -(4-C₆H₄)—SO₂NH—CH₂CH₂—S—S—CH₂CH₂—NHSO₂-(4-C₆H₄)—groups.

Example 151

[0290] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.2-(4-aminophenyl)-1,3-dithiane was prepared following a modification tothe procedure described in Truce, W.; Roberts, F J. Org. Chem. 1963, 28,961. To a well-stirred mixture of 4-acetamidobenzaldehyde (12.7 g) in200 mL of acetic acid was added MgCl₂ (5.57 g) followed by 1,3-propanedithiol (8.44 g). The reaction mixture turned white upon addition of thedithiol. This mixture was stirred at room temperature for 2 hours. Thewhite precipitate was isolated by filtration, washed several times withwater, and dried to give 12.5 g of 2-(4-acetamidophenyl)-1,3-dithiane.

[0291] All 12.5 g of 2-(4-acetamidophenyl)-1,3-dithiane was dissolved in150 mL of ethanol. A total of 150 mL of 2N HCl was added, and thereaction mixture was heated to reflux. After reacting at thistemperature for 6 hours, the clear yellow solution was allowed to coolto room temperature and then made basic with a dilute NaOH solution. Theresulting light yellow precipitate was isolated by filtration, washedwith water until neutral, and dried to yield 14.8 g of the desired2-(4-aminophenyl)-1,3-dithiane.

[0292] 2-4-aminophenyl)-1,3-dithiane (7.13 g), prepared as describedabove, was added to 250 mL of water containing 6.83 g of 37% HCl and wascooled in an ice bath. A solution of 2.52 g NaNO₂ dissolved in 125 mL ofwater was added. This mixture was added in one portion to a rapidlystirring slurry of carbon black pellets (225 g) in 2 liters of watercontaining 200 g of ice. The slurry was stirred for 4.5 hours andfiltered to collect the carbon black product. This product was washedwith water, collected by filtration, and dried at 125° C. to a constantweight.

[0293] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.65% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.07mmol/g of attached -(4-C₆H₄)-2-(1,3-dithiane) groups.

Example 152

[0294] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.2-(4-aminophenyl)-1,3-dithiane (4.75 g), prepared as described inExample 151 above, was added to 250 mL of water containing 4.55 g of 37%HCl. Next, the mixture was cooled in an ice bath and a solution of 1.68g NaNO₂ dissolved in 125 mL of water was added. The resulting mixturewas added in one portion to a rapidly stirring slurry of carbon blackpellets (112.5 g) in 2 liters of water containing 100 g of ice. Theslurry was stirred for 4.5 hours and filtered to collect the carbonblack product. This product was washed with water, collected byfiltration, and dried at 125° C. to a constant weight.

[0295] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.47% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.04mmol/g of attached -(4-C₆H₄)-2-(1,3-dithiane) groups.

Example 153

[0296] This example further illustrates the in situ preparation of acarbon black product of the present invention. A carbon black with aniodine number of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0297] N,N′-bis-(4-aminophenyl)-piperazinosulfenamide was prepared asfollows. A solution of 12 (21.6 g) in 800 mL of ethanol was added to awell-stirred solution of 4,4-diaminophenyldisulfide (21.3 g) andpiperazine (36.7 g) in 1 liter of ethanol at room temperature. The darkcolored reaction mixture was stirred at this temperature for 16 hoursand then filtered. The cream colored precipitate was washed with waterand filtered to yield 25.1 g of the desiredN,N′-bis-(4-aminophenyl)-piperazinosulfenamide.

[0298] N,N′-bis-(4-aminophenyl)-piperazinosulfenamide (11.2 g), preparedas described above, was added to a well-stirred mixture of carbon black(225 g), ice (280 g), and water (2 liters). To this was added a solutionof 5.04 g NaNO₂ dissolved in 75 mL of water followed by a solution of37% HCl (13.65 g) in 75 mL of water. The slurry was stirred overnightand filtered to collect the carbon black product. The product was washedwith water, filtered, and dried at 125° C. to a constant weight.

[0299] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.91% sulfur, compared to 1.21%for the untreated black. Therefore, the carbon black product had 0.11mmol/g of attached -(4-C₆H₄)—S-(1,4-C₄H₈N₂)—S-(4-C₆H₄)— groups.

Example 154

[0300] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0301] Bis(4-aminophenyl) disulfide (4.19 g) was dissolved in 230 mL ofwater containing 7.32 g of 37% HCl. The solution was then cooled in anice bath and a solution of 2.64 g NaNO₂ dissolved in 40 mL of wateradded. This mixture was added in one portion to a rapidly stirringslurry of carbon black pellets (225 g) in 1200 mL of water containing asmall amount of ice. The slurry was stirred for 2 hours and filtered tocollect the carbon black product. This product was washed with ethanol,then with water, collected by filtration, and dried at 125° C. to aconstant weight.

[0302] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.55% sulfur, compared to 1.10%for the untreated black. Therefore, the carbon black product had 0.07mmol/g of attached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 155

[0303] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0304] Bis(4-aminophenyl) disulfide (8.55 g) was dissolved in 180 mL ofwater containing 14.65 g of 37% HCl. The solution was then cooled in anice bath and 50 mL of ethanol was added followed by addition of asolution of 5.28 g NaNO2 dissolved in 35 mL of water. This mixture wasadded in several portions to a rapidly stirring slurry of carbon blackpellets (225 g) in 1200 mL of water containing a small amount of ice.The slurry was stirred for 2 hours and filtered to collect the carbonblack product. This product was washed with ethanol, then with water,collected by filtration, and dried at 125° C. to a constant weight.

[0305] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 1.82% sulfur, compared to 1.10%for the untreated black. Therefore, the carbon black product had 0.11mmol/g of attached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 156

[0306] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/1100 g was used.

[0307] Bis(4-aminophenyl) disulfide (11.18 g) was dissolved in 560 mL ofwater containing 19.53 g of 37% HCl. The solution was cooled in an icebath and a solution of 7.04 g NaNO2 dissolved in 60 mL of water added.An additional 150 mL of water was added, and the mixture added in oneportion to a rapidly stirring slurry of carbon black pellets (225 g) in1200 mL of water containing a small amount of ice. The slurry wasstirred for 2 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight.

[0308] A sample of the carbon black product which had been extractedwith THF overnight and dried contained 2.26% sulfur, compared to 1.10%for the untreated black. Therefore, the carbon black product had 0.18mmol/g of attached -(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 157

[0309] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/1100 g was used.

[0310] Bis(4-aminophenyl) disulfide (13.97 g) was dissolved in 560 mL ofwater containing 24.4 g of 37% HCl. The solution was cooled in an icebath and a solution of 8.80 g NaNO2 dissolved in 60 mL of water added.An additional 150 mL of water was added and the resulting mixture addedin one portion to a rapidly stirring slurry of carbon black pellets (225g) in 1200 mL of water containing a small amount of ice. The slurry wasstirred for 3.5 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight. A sample of thecarbon black product which had been extracted with THF overnight anddried contained 2.50% sulfur, compared to 1.10% for the untreated black.Therefore, the carbon black product had 0.22 mmol/g of attached-(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 158

[0311] This example further illustrates the preparation of a carbonblack product of the present invention. A carbon black with an iodinenumber of 120 mg/g and a DBPA of 125 mL/100 g was used.

[0312] Bis(4-aminophenyl) disulfide (17.1 g) was dissolved in 175 mL ofwater containing 29.30 g of 37% HC 1. The resulting solution was cooledin an ice bath and a solution of 10.6 g NaNO2 dissolved in 60 mL ofwater added. 100 mL of ethanol was added, and this mixture was added inone portion to a rapidly stirring slurry of carbon black pellets (225 g)in 1200 mL of water containing a small amount of ice. The slurry wasstirred for 2 hours and filtered to collect the carbon black product.This product was washed with ethanol, then with water, collected byfiltration, and dried at 125° C. to a constant weight. A sample of thecarbon black product which had been extracted with THF overnight anddried contained 2.55% sulfur, compared to 1.10% for the untreated black.Therefore, the carbon black product had 0.23 mmol/g of attached-(4-C₆H₄)—S—S-(4-C₆H₄)— groups.

Example 159 Comparative Carbon Black Products

[0313] In this comparative example, the carbon black used in Example118-158 was washed with water, ethanol and water and subsequently driedto give the comparative carbon black product.

Example 160 Comparative Carbon Black Products

[0314] In this comparative example, the carbon black used in Examples118-158 was used without modification and serves as the comparativecarbon black product.

[0315] Use of Carbon Black Products in Rubber Formulations

[0316] The carbon black products described in Examples 118-158 can beused in a variety of elastomers. The elastomers include, but are notlimited to, the following types: solution SBR, functionalized (tincoupled and/or chemically modified and/or other functional-ization)solution SBR, natural rubber, emulsion SBR, polybutadiene, andterpolymers. These elastomers may appear in rubber formulations alone oras blends. NS 116 and NS 114 are chemically modified tin coupledsolution SBRs available from Nippon Zeon, Japan. Duradene 715 is asolution SBR. Duradene is a registered trademark for SBR productsavailable from Firestone, Akron Ohio. S 1216 is a solution SBR availablefrom Goodyear Tire and Rubber Co., Akron Ohio. SBR-1500 is an emulsionSBR available from Copolymer Rubber and Chemical Corp., Baton Rouge, La.SL-574 is a tin coupled solution SBR available from Japan SyntheticRubber Co. (JSR), Japan. RCT0586 and T0587 are chemically modifiedsolution SBRs also available from JSR. Flexzone is a registeredtrademark for antidegradent products available from Uniroyal Chemical,Naugatuck, Conn. CBS is N-cyclohexylbenzothiazylsulfenamide, MBT is2-mercaptobenzothiazole and DTDM is N,N′-dithiodimorpholine.

Examples 161-166

[0317] These examples illustrate the use of the carbon black products ofExamples 118, 121, 122 and the comparative Example 160 in two differentrubber formulations. The polymer was milled in a Brabender mixer for 1minute at 100° C. The carbon black product or comparative carbon blackwas added and mixed for 3 additional minutes or until a temperature of160° C. was reached. The mixture was then dumped and passed through anopen mill 3 times. After allowing the compound to stand at roomtemperature for 2 hours, it was transferred back into the Brabender andmixed for 1 minute at 100° C. After 1 minute, ZnO and stearic acid wereadded and mixed for 2 minutes and then Flexzone 7P antidegradent wasadded and mixed for an additional minute or until a temperature of 160°C. was reached. The sample was then dumped, passed through an open mill3 times and allowed to stand at room temperature for 2 hours. The samplewas placed back into the Brabender and mixed for 1 minute at 100° C. Thecuratives were then added and mixed for 1 minute and the sample thendumped and passed through an open mill 3 times. The formulations usedwere selected from Table I.

[0318] The data in Table II show that carbon black products of thepresent invention are useful in rubber formulations. In the case where ablend of NS-116 and NS-114 was used, significant increases in 100%modulus, bound rubber, tensile strength, hardness and abrasionresistance can be obtained, as can significant decreases in Tan δ. InDuradene 715, higher modulus, hardness, and bound rubber are obtained,while tensile strength, elongation at break and 70° C. Tan δ arereduced. The magnitude of the effect depends on the specific groupsattached to the carbon black product.

Examples 167-180

[0319] These examples illustrate the use of the carbon black products ofExamples 121-124 and the comparative Example 160 in several differentrubber formulations. With the exception of those formulations containingDTDM, rubber compounds were prepared by the method described forExamples 161-166 using formulations selected from Table I. A slightchange in the mixing procedure was made for those rubber compoundscontaining DTDM. In this case, the samples with DTDM were mixed for 3minutes after addition of the Flexzone 7P, after which, the mixingprocedure described for Examples 161-166 was followed.

[0320] The performance data in Table II show that carbon black productsaccording to the invention are useful in several different rubberformulations. In particular, carbon black products described in Examples4 and 5 reduce 70° C. Tan δ when using natural rubber, SBR-1500, orDuradene 715 in the formulation. Furthermore, addition of 0.8 phr ofDTDM to the rubber formulations containing carbon black products ofExamples 4 and 5 gives vulcanizates with higher hardness, modulus, andbound rubber, relative to the formulation without DTDM. It also resultsin lower elongation and 70° C. Tan δ and, in general, gives greatertensile strength and improved abrasion resistance.

Examples 181-188

[0321] These examples illustrate the use of the carbon black products ofExamples 120, 126, 139 and 140 and the comparative Example 160 inseveral different rubber formulations. The rubber compounds wereprepared by the method described for Examples 161-166 using formulationsselected Table I.

[0322] The performance data in Table IV show that carbon black productsaccording to the invention are useful in several different rubberformulations. Specifically, in a blend of NS-116 and NS-114, use ofcarbon black products from Examples 120, 126, 139 amd 140 gave increasedbound rubber and significant reductions in 70° C. Tan δ. In Duradene,carbon black products described in Examples 9 and 23 are especiallyuseful in reducing 70° C. Tan δ.

Examples 189-196

[0323] These examples illustrate the use of the carbon black products ofExamples 123, 127, 134 and 136 and the comparative Example 159 inseveral different rubber formulations. The rubber compounds wereprepared by the following method using formulations selected from Table1.

[0324] The polymer was milled in a Brabender mixer for 1 minute at 100°C. A mixture of ZnO and the carbon black product or comparative carbonblack was added and mixed for 2 additional minutes. The stearic acid andFlexzone 7P antidegradent were added and mixed for 2 additional minutes.The sample was dumped and passed through an open mill 3 times. Thesample was allowed to cool and then transferred back into the Brabendermixer and mixed for 1 minute at 100° C. The curative package was thenadded, mixing continued for 1 minute, and the sample dumped then passedthrough a open mill 3 times.

[0325] Table V shows that these carbon black products are useful inseveral rubber formulations including functionalized andunfunctionalized solution SBRs. Furthermore, use of carbon black productdescribed in Example 123 in S-1216, Duradene 715, and NS-116 results inlower 70° C. Tan δ values as well as increased bound rubber. Whencompounded with NS-114, the carbon black product from Example 127 gavehigher modulus, bound rubber and abrasion resistance, lower elongationand 70° C. Tan δ, and equal tensile strength and hardness.

Examples 197-200

[0326] These examples illustrate the use of the carbon black products ofExamples 129 and 135 and the comparative Example 160 in two differentrubber formulations. The rubber compounds were prepared by the themethod described in Examples 189-196 using formulations selected fromTable I.

[0327] Table VI shows that these carbon black products are useful inthese rubber formulations using functionalized or unfunctionalizedsolution SBRs. When using a blend of NS-116 and NS-114, increases inmodulus, hardness, and bound rubber were observed. Sizable decreases in70° C. Tan δ and elongation are also seen. In Duradene 715, modulus wasincreased while tensile strength, elongation at break, and 70° C. Tan 6are all substantially reduced.

Examples 201-205

[0328] These examples illustrate the use of the carbon black products ofExample 155 and the comparative Example 160 in different rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 189-196 using formulations selected from Table I.

[0329] Table VII shows that this carbon black product was useful in anumber of rubber formulations, specifically formulations that containedNR, emulsion SBR, or a functionalized solution SBRs selected fromSL-574, RCTO-586, or TO-587.

Examples 206-215

[0330] These examples illustrate the use of the carbon black products ofExamples 154-158 and the comparative Example 159 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 189-196 using formulations selected from Table I.

[0331] As can be seen by inspection of the data in Table VIII below, awide range of treatment levels as exemplified by the carbon blackproducts in Examples 154-158 can have an impact on rubber performanceproperties.

Examples 216-221

[0332] These examples illustrate the use of the carbon black products ofExamples 137, 138, and 141 and the comparative Example 160 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table 1.

[0333] Table IX shows that these carbon black products were useful inseveral rubber formulations including functionalized andunfunctionalized solution SBRs. In particular, the carbon black productsin Examples 137, 138, and 141 all showed lower 70° C. Tan δ values aswell as increased bound rubber in both rubber systems. In addition, theproducts in Example 137 and 138 also showed improvements in abrasionresistance.

Examples 222-235

[0334] These examples illustrate the use of the carbon black products ofExamples 142-147 and the comparative Example 160 in three rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

[0335] Table X shows that these carbon black products were useful in therubber formulations studied. In particular, all of the blacks studiedshowed reductions in 70° C. Tan δ values and increased bound rubber inboth functionalized and unfunctionalized solution SBRs with comparablehardness. Comparable hardness and 70° C. Tan δ values were found innatural rubber, with the carbon black product of Example 146 showing thegreatest reduction in Tan δ.

Examples 236-246

[0336] These examples illustrate the use of the carbon black products ofExamples 148-153 and the comparative Example 160 in two rubberformulations. The rubber compounds were prepared by the the methoddescribed in Examples 161-166 using formulations selected from Table I.

[0337] Table XI shows that these carbon black products were useful inrubber formulations. For example, when the carbon black products ofExample 148, 149, and 153 were compounded in Duradene 715 or a 70/30blend of NS-116 and NS-114, in general, abrasion resistance is eitherunchanged or improved while 70° C. Tan δ values were reduced.

Examples 247-262

[0338] These examples illustrate the use of the carbon black products ofExamples 119, 125, 128 and 130-133 and the comparative Example 160 invarious rubber formulations. The rubber compounds were prepared by thethe method described in Examples 161-166 using formulations selectedfrom Table I.

[0339] Table XII shows that these carbon black products were useful inrubber formulations. For example, when the carbon black product ofExample 119 was compounded with Duradene 715, SBR-1500, or a blend ofNS-116 and NS-114, abrasion resistance was improved while 70° C. Tan δvalues were reduced and the percentage of bound rubber increased. Use ofcarbon black products from Examples 130-133 in Duradene 715 and NaturalRubber showed that a wide range of carbon black treatment levels of thistype can have an impact on rubber performance properties.

Example 263 Preparation of a Carbon Black Product

[0340] Ten grams of a carbon black with a surface area of 230 m2/g and aDBPA of 70 m2/g was added to a stirring solution of 3.06 g of3-amino-N-ethylpyridinium bromide in 72 g of water. Concentrated nitricacid (1.62 g) was added, and the mixture was stirred and heated to about70° C. A solution of 1.07 g NaNO₂ in about 5 g of water was added over afew minutes. The diazonium salt N₂C₅H₄N(C₂H₅)⁺⁺ was formed in situ,which reacted with the carbon black. After the reaction mixture wasstirred for one hour, the sample was dried in an oven at 125°. Theproduct had a mean volume particle size of 0.18 microns. The product hadattached 3-C₅H₄N(C₂H₅)+groups.

Example 264 Preparation of a Carbon Black Product

[0341] 3-Amino-N-methylpyridinium iodide (3.92 g) was dissolved in 70 gof water. A solution of 2.58 g AgNO₃ in 6 g of water was added. Afterstirring for 15 minutes, the precipitate was removed by filtration and10 g of a carbon black with a surface area of 230 m2/g and a DBPA of 70m2/g was added. Concentrated nitric acid (1.62 g) was added, and themixture was stirred and heated to about 70°. A solution of 1.07 g NaNO₂in about 5 g of water was added over a few minutes. The diazonium saltN₂C₅H₄CH₂N(CH₃)++was formed in situ, which reacted with the carbonblack. Bubbles were released. After the reaction mixture was stirred forabout 40 minutes at 70 o and then boiled for about 15 minutes. Thesample was dried in an oven at 125°. The product had a mean volumeparticle size of 0.23 microns. The product had a 325 mesh residue of0.0% compared to 94% for the untreated carbon black. The product hadattached 3-C₅H₄N(CH₃)⁺ groups.

Example 265 Preparation of a Carbon Black Product

[0342] Fifty grams of benzyltrimethylammonium chloride was added over 25minutes to cold 90% nitric acid. The mixture was kept below 10° C. forfive hours. Ice (500 g) was added, and the mixture was neutralized withKOH. The precipitate was removed by filtration. Ethanol (IL) was addedand the mixture was filtered again. 3-Nitrobenzyltrimethylammoniumnitrate was recovered from the filtrate. This material was 75% pure byNMR. A mixture of 10 g of 3-Nitrobenzyltrimethylammonium nitrate, 14 gFe filings, 2 g of concentrated HCl and 400 g of water was boiled for2.5 hr. The mixture was neutralized with KOH and filtered to give anaqueous solution of 3-aminobenzyltrimethylammonium nitrate/chloride.

[0343] Fourteen grams of carbon black with a surface area of 230 m2/gand a DBPA of 70 m2/g was added to a stirring solution of 3.06 g of3-aminobenzyltrimethylammonium nitrate/chloride in 72 g of water.Concentrated nitric acid (1.62 g) was added, and the mixture was stirredand heated to about 70° C. A solution of 1.07 g NaNO₂ in about 5 g ofwater was added over a few minutes. The diazonium salt 3-N₂C₆H₄N(CH₃)was formed in situ, which reacted with the carbon black. After thereaction mixture was stirred for one hour, the sample was dried in anoven at 125° C. The product had a mean volume particle size of 0.18microns. The product had attached 3-N₂C₆H₄CH₂N(CH₃)₃+groups.

Example 266 Preparation of a Carbon Black Product

[0344] Silver nitrite (30.9 g) was added to a solution of 41.4 g ofN-(4-aminophenyl)pyridinium chloride in 700 g of water and the mixturewas stirred at 70 for 1 ½ hours. The mixture was filtered and 200 g of acarbon black with a surface area of 200 m2/g and a DBPA of 122 mL/100 gwas added. An additional one liter of water and 20 g of concentrated HClwere added. The diazonium salt N₂C₆H₄C₅H₅ ⁺⁺ was formed in situ, whichreacted with the carbon black. Bubbles were released. The dispersion wasstirred at 70-80 for 2 ½ hours and then dried in an oven at 125° C. Theproduct had attached C₆H₄NC₅H₅ ⁺ groups.

Example 267 Preparation of a Carbon Black Product

[0345] In a modification of a procedure from U.S. Pat. No. 2,821,526, amixture of 250 g p-acetaminophenacyl chloride, 65 g of trimethylamineand about 600 g of water was stirred for three days at room temperature.An additional 5 g of trimethylamine in 15 g water was added and themixture was heated at 60° for two hours. After cooling and filtering,201 g concentrated HCl was added and the solution was boiled for anhour. After cooling, 4L of acetone was added and4-aminophenacyltrimethylammonium chloride hydrochloride was collected asa solid. 4-Aminophenacyltrimethylammonium chloride hydrochloride (10.1g) was suspended in 50 mL of ethanol. After addition of 4.1 gtriethylamine, the mixture was stirred for 40 minutes and heated atreflux for one hour. 4-Aminophenacyl-trimethylammonium chloride wascollected by filtration and washed with ethanol.

[0346] 4-Aminophenacyltrimethylammonium chloride (2.51 g) was dissolvedin water. Silver nitrite (1.69 g) was added, and the mixture was heatedat 70 o for one hour. After filtering off the precipitate, 10 g of acarbon black with a surface area of 230 m2/g and a DBPA of 70 mL/100 gwas added. Water was added to bring the volume up to about 100 mL.Concentrated HCl (1.1 g) was added and the dispersion was heated withstirring at 70° for one hour. The diazonium salt N₂C₆H₄COCH₂N(CH₃)₃ ⁺⁺was formed in situ, which reacted with the carbon black. Bubbles werereleased. The product had attached C₆H₄COCH₂N(CH₃)₃ ⁺ groups.

Example 268 Preparation of a Carbon Black Product

[0347] A solution of 2.12 g of 4-acetaminophenacyl chloride, 0.83 g ofpyridine and 6.4 g of dimethylsulfoxide was stirred overnight. Afteraddition of an additional 0.8 g of pyridine and 1 g ofdimethylsulfoxide, the solution was stirred an additional 5 hours. Ether(50 mL) was added, and acetamidophenacylpyridinium chloride wascollected by filtration. The acetamidophenacylpyridinium chloride wasdissolved in water, the solution filtered and 1.7 g concentrated HCl wasadded. After boiling for one hour, the solution was cooled, acetone wasadded, and 4-aminophenacylpyridinium chloride hydrochloride wascollected by filtration. Two grams of 4-aminophenacylpyridinium chloridehydrochloride was dissolved in 15 g water and 4.5 g of a basic ionexchange resin (Amberlite IRA400-OH) was added. After stirring, theresin was removed by filtration and 4-aminophenacylpyridinium chloridewas collected as an aqueous solution.

[0348] A solution of 1.3 g of 4-aminophenacylpyridinium chloride in 25 gof water was heated at reflux with 1 g silver nitrite for about 90minutes. The precipitate was removed by filtration. Five grams of acarbon black with a surface area of 200 m2/g and a DBPA of 122 ML/100 gwere added and the mixture was heated to about 80°. Concentrated HCl(0.52 g) was added and the dispersion was stirred an additional 1 ½hours. The diazonium salt N₂C₆H₄COCH₂(NC₅H₅)⁺⁺ was formed in situ, whichreacted with the carbon black. The product had attachedC₆H₄COCH₂(NC₅H₅)⁺ groups. TABLE I Rubber Formulations Formulation A B CD E F G H I J K L M N NS-116 100 80 70 NS-114 100 20 30 Duradene 715 100100 Natural Rubber 100 100 SBR-1500 100 100 S-1216 100 SL-574 100RCTO-586 100 TO-587 100 CB Product or 50 50 50 50 50 50 50 50 50 50 5050 50 50 Comparative DTDM 0.8 0.8 0.8 ZnO 3 3 3 3 3 3 3 3 3 3 3 3 3 3Stearic Acid 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Flexzone 7P 1 1 1 1 1 1 1 1 1 11 1 1 1 CBS 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.251.25 1.25 MBT 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2Sulfur 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.751.75 Total 159.2 159.2 159.2 159.2 159.2 160 159.2 160 159.2 160 159.2159.2 159.2 159.2

[0349] TABLE II Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 161 118 D 4.4121.38 21.54 305 74 44 0.640 0.126 124 153 162 121 D 4.14 — 20.96 278 7354.7 0.642 0.106 137 189 163 122 D 4.18 20.01 20.72 309 74 44.3 0.6340.117 108 139 Comp. 160 D 3.69 — 14.34 257 71 35.7 0.613 0.160 100 100164 118 E 4.20 — 15.07 242 74 46.8 0.455 0.142 81 106 165 121 E 5.66 —15.62 214 77 53.8 0.439 0.135 75 107 166 122 E 4.10 — 14.98 254 74 46.70.416 0.135 73 106 Comp. 160 E 2.89 15.14 24.02 435 70 45.4 0.414 0.178100 100

[0350] TABLE III Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 167 121 G 3.6618.21 27.59 472 69 48.0 0.235 0.121 104 101 168 121 H 3.87 19.32 28.16436 71 51.9 0.210 0.102 100 115 169 122 G 3.47 16.60 28.94 516 70 46.00.249 0.111 87 90 170 123 H 3.16 15.57 28.30 518 70 42.6 0.241 0.146 9190 171 124 G 3.55 16.75 29.67 519 71 42.4 0.244 0.155 102 96 Comp. 160 G3.55 17.87 29.56 489 70 47.3 0.257 0.123 100 100 172 121 I 3.42 18.8225.11 386 72 40.7 0.297 0.159 107 116 173 121 J 3.90 21.38 22.72 316 7446.9 0.281 0.143 105 140 174 122 I 3.09 15.41 25.73 464 73 37.2 0.2940.173 91 114 175 122 J 3.85 20.57 21.07 317 74 45.2 0.275 0.135 98 127176 124 I 3.98 18.60 22.40 354 73 35.7 0.279 0.172 90 103 Comp. 160 I2.91 15.76 25.36 438 70 34.7 0.322 0.180 100 100 177 121 E 4.62 — 14.57283 77 44.1 0.365 0.135 66 108 178 121 F 4.11 — 16.15 241 74 49.8 0.4580.130 104 130 179 122 E 3.89 — 16.72 287 74 43.5 0.410 0.140 79 117 180122 F 4.26 — 16.91 257 75 46.3 0.406 0.127 94 139 Comp. 160 E 3.17 16.8820.52 350 72 39.6 0.421 0.161 100 100

[0351] TABLE IV Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 181 120 D 3.68— 16.32 278 73 45.3 0.640 0.135 80 93 182 126 D 3.16 16.20 19.55 349 7355.8 0.630 0.122 87 94 183 139 D 3.56 15.87 18.09 334 74 47.1 0.6480.124 98 81 184 140 D 3.02 15.13 19.97 373 72 46.3 0.662 0.135 103 95Comp. 160 D 3.60 16.88 20.58 354 75 39.9 0.622 0.166 100 100 185 120 E3.03 14.74 16.92 334 74 45.7 0.459 0.162 99 94 186 126 E 3.87 — 12.84238 75 49.9 0.460 0.146 84 120 187 139 E 3.30 — 14.76 296 75 46.4 0.3960.137 63 100 188 140 E 2.41 11.60 18.34 428 72 45.5 0.409 0.170 70 101Comp. 160 E 3.15 — 15.06 283 73 44.1 0.468 0.163 100 100

[0352] TABLE V Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 189 123 K 4.8518.31 18.56 312 65 30.2 0.373 0.168 85 99 190 134 K 3.87 15.50 20.65 38364 25.8 0.395 0.177 89 66 Comp. 159 K 4.01 17.03 19.64 336 62 27.3 0.4500.176 100 100 191 123 E 4.25 — 15.07 260 62 32.3 0.375 0.175 88 110 192134 E 4.61 18.50 21.80 349 60 29.4 0.401 0.198 90 91 Comp. 159 E 4.9619.73 20.66 315 59 30.7 0.430 0.194 100 100 193 123 B 3.62 — 23.33 38669 30.86 0.278 0.141 92 104 Comp. 159 B 3.42 — 23.41 402 69 28.36 0.2970.146 100 100 194 127 B 4.04 — 18.52 294 60 35 0.289 0.137 110 113 Comp.159 B 3.25 14.09 18.36 385 60 28.1 0.327 0.173 100 100 195 136 B 3.61 —20.94 447 62 27.7 — 0.165 59 79 Comp. 159 B 3.53 — 22.08 387 63 24.2 —0.157 100 100 196 136 E 5.10 — 15.57 284 63 26.3 — 0.171 41 74 Comp. 159E 4.54 — 20.56 316 63 21.4 — 0.179 100 100

[0353] TABLE VI Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 197 129 C 3.2914.57 19.99 389 75 37.7 0.665 0.142 90 116 198 135 C 3.01 13.66 18.03372 75 43.2 0.648 0.141 89 106 Comp. 160 C 2.85 12.78 19.13 408 74 32.80.668 0.173 100 100 199 129 E 3.24 — 12.90 272 77 36.1 0.405 0.162 80117 200 135 E 4.36 — 11.08 239 79 31.0 0.379 0.165 49 81 Comp. 160 E2.80 13.65 22.23 447 75 33.9 0.448 0.178 100 100

[0354] TABLE VII Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 201 155 I 3.5614.91 23.63 468 74 33.8 0.291 0.192 83 85 Comp. 160 I 3.40 15.57 26.95492 74 34.2 0.327 0.201 100 100 202 155 G 2.77 14.19 30.13 567 72 34.10.239 0.129 87 84 Comp. 160 G 3.76 17.91 31.15 504 72 43.2 0.241 0.117100 100 203 155 L 3.77 13.36 19.14 325 75 39.1 0.273 0.124 92 114 Comp.160 L 2.96 13.39 21.22 430 73 37.3 0.300 0.149 100 100 204 155 M 3.2310.31 14.09 420 74 17.9 0.790 0.179 68 73 Comp. 160 M 2.61 9.50 17.64525 71 17.5 0.819 0.246 100 100 205 155 N 3.22 13.19 23.12 536 78 330.332 0.185 104 103 Comp. 160 N 3.83 15.06 19.54 408 80 27.1 0.354 0.225100 100

[0355] TABLE VIII Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 206 154 A 4.0817.75 22.13 362 63 37.5 0.792 0.173 101 134 207 155 A 3.95 16.96 22.13376 63 37.5 0.814 0.178 95 150 208 156 A 3.74 15.15 15.66 300 62 41.10.785 0.149 86 152 209 157 A 4.02 — 14.59 290 62 37.2 0.776 0.150 72 141210 158 A 3.46 — 16.42 357 61 32.8 0.783 0.180 84 130 Comp. 159 A 3.7615.25 19.94 375 67 24.6 0.777 0.233 100 100 211 154 E 6.08 — 14.39 21263 30.7 0.377 0.160 71 128 212 155 E 6.78 — 12.30 178 66 24.9 0.3250.148 51 91 213 156 E 6.28 — 11.10 175 66 25.2 0.322 0.156 54 100 214157 E 5.90 — 10.62 187 68 23.4 0.309 0.166 47 83 215 158 E 5.95 — 11.06190 66 27.0 0.315 0.168 53 91 Comp. 159 E 4.96 19.73 20.66 315 59 30.70.430 0.194 100 100

[0356] TABLE IX Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 216 137 D 4.2122.24 23.04 310 73 44.3 0.591 0.127 94 111 217 138 D 4.11 21.64 26.69323 74 44.0 0.670 0.123 99 111 Comp. 160 D 4.14 — 17.62 268 74 37.50.615 0.141 100 100 218 141 D 3.98 18.90 19.23 305 73 44.9 0.611 0.11894 80 Comp. 160 D 4.05 19.56 22.38 337 72 38.3 0.586 0.142 100 100 219137 E 3.81 — 16.55 251 73 46.3 0.450 0.135 127 141 220 138 E 4.00 —16.16 241 74 46.1 0.440 0.138 114 131 Comp. 160 E 3.74 — 17.56 272 7339.7 0.312 0.157 100 100 221 141 E 4.06 — 13.38 260 75 43.5 0.378 0.15861 75 Comp. 160 E 3.30 17.38 20.65 344 71 42.5 0.481 0.163 100 100

[0357] TABLE X Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 222 142 E 3.8218.49 19.75 319 73 42.7 0.488 0.152 76 101 223 143 E 3.49 16.70 18.96332 73 42.2 0.466 0.164 77 108 224 144 E 3.57 17.49 18.68 316 73 42.40.477 0.150 66 120 225 145 E 3.35 17.23 18.56 328 73 41.6 0.531 0.160 6497 Comp. 160 E 3.21 16.19 21.51 377 72 41.2 0.494 0.169 100 100 226 142D 3.68 18.53 22.54 353 72 41.8 0.650 0.118 81 99 227 143 D 3.62 17.8522.62 366 72 43.1 0.664 0.134 89 108 228 144 D 3.68 — 13.36 239 72 44.40.655 0.125 96 105 229 145 D 3.92 — 15.80 259 72 42.9 0.678 0.126 81 99230 146 D 3.72 18.91 22.08 340 72 43.7 0.860 0.128 84 104 231 147 D 3.87— 17.90 285 72 45.1 0.643 0.119 84 109 Comp. 160 D 3.73 17.51 20.16 33673 40.0 0.682 0.155 100 100 232 142 G 3.47 16.49 27.76 489 70 43.3 0.2810.148 74 86 233 145 G 3.44 16.45 27.80 495 70 43.8 0.251 0.145 74 46 234146 G 3.44 16.57 27.53 488 70 44.0 0.248 0.139 72 85 235 147 G 3.8917.81 28.28 478 71 44.4 0.267 0.156 76 92 Comp. 160 G 3.88 18.40 28.78470 71 49.1 0.262 0.146 100 100

[0358] TABLE XI Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 236 148 D 3.6518.36 21.30 339 73 43.6 0.603 0.122 120 101 237 149 D 3.60 — 17.24 28773 43.7 0.635 0.124 120 114 238 150 D 3.67 — 15.47 280 73 36.7 0.6470.120 85 76 239 151 D 3.74 17.65 20.99 348 73 38.9 0.618 0.149 133 115240 152 D 3.36 16.50 20.77 358 73 40.1 0.651 0.148 117 94 241 153 D 3.83— 16.08 263 73 51.0 0.589 0.111 104 108 Comp. 160 D 3.76 18.94 20.39 31873 38.4 0.624 0.138 100 100 242 148 E 3.52 15.21 15.87 266 73 49.3 0.4300.136 93 134 243 149 E 3.18 — 15.40 280 73 46.5 0.431 0.145 104 113 244150 E 3.48 — 15.57 292 73 38.4 0.412 0.140 68 95 245 151 E 2.81 14.3519.54 382 71 43.5 0.446 0.172 95 112 246 153 E 4.96 — 10.63 173 78 39.80.406 0.136 53 100 Comp. 160 E 2.79 — 12.87 261 70 45.6 0.462 0.164 100100

[0359] TABLE XII Carbon 100% 300% Abrader Abrader Black Modulus ModulusTensile Hardness Bound Tan_δ Tan_δ Index 14% Index 21% Ex. Prod. Form.Mpa Mpa Mpa Elong. Shore A Rubber 0° C. 70° C. Slip Slip 247 119 E 3.63— 14.43 246 74 46.1 0.439 0.142 107 126 248 125 E 3.06 16.33 19.15 34272 40.2 0.446 0.150 111 102 249 130 E 4.38 — 14.69 247 76 42.0 0.4390.134 75 105 250 131 E 3.93 — 17.69 289 74 43.2 0.389 0.136 88 107 251132 E 4.17 — 16.88 266 74 47.4 0.460 0.136 101 177 252 133 E 3.52 —19.18 318 73 43.3 0.475 0.142 103 105 Comp. 160 E 3.26 17.08 22.91 38371 38.6 0.439 0.164 100 100 253 119 D 3.70 — 19.08 299 73 45.6 0.6910.127 109 133 254 128 D 3.88 18.01 20.4 333 74 39.4 0.462 0.129 77 110Comp. 160 D 3.41 17.06 20.35 344 73 37.6 0.622 0.152 100 100 255 119 I3.38 18.8  22.68 350 72 41.1 0.272 0.151 113 114 256 130 I 3.55 16.9323.73 396 71 37.2 0.293 0.169 104 111 Comp. 160 I 3.09 16.08 23.46 40771 34.7 0.327 0.179 100 100 7% Slip 14% Slip 257 119 G 3.56 17.13 29.20505 71 37.9 0.256 0.132 96 105 258 125 G 3.21 15.94 28.87 529 69 37.90.249 0.139 92 92 259 130 G 3.27 16.55 27.70 505 69 41.5 0.233 0.115 97106 260 131 G 3.20 16.58 29.30 509 69 42.0 0.236 0.123 103 110 261 132 G3.32 16.65 26.82 485 70 43.6 0.250 0.153 103 108 262 133 G 3.19 16.3628.72 508 69 42.4 0.251 0.128 93 93 Comp. 160 G 3.57 18.29 28.09 472 7041.7 0.252 0.127 100 100

Example 269 Preparation of a Carbon Black Product

[0360] A cold solution of 3.56 g NaNO₂ in water was added to a solutionof 10.2 g 4,4′-methylenedianiline, 140 g of water and 19.7 g ofconcentrated HCl that was stirring in an ice bath. After stirring forabout 15 minutes, the resulting solution of the diazonium salt was addedto a suspension of 200 g of a carbon black in 1.6 L of water that wasstirring at room temperature. The carbon black had a surface area of 55m2/g and DBPA of 46 mL/100 g. After stirring for 1 ½ hours, the mixturewas neutralized with NaOH and filtered. The carbon black product waswashed with water and dried in an oven at 125° C. The carbon blackproduct contained 0.332% nitrogen after Soxhlet extraction overnightwith THF, compared to 0.081% nitrogen for the untreated carbon black.Therefore, the carbon black product had 0.18 mmol/g of attachedC₆H₄CH₂C₆H₄NH₂ groups.

The claimed invention is:
 1. A process for preparing a carbon blackproduct having an organic group attached to the carbon black comprisingthe step of: reacting at least one diazonium salt with a carbon black inthe absence of an externally applied electric current sufficient toreduce the diazonium salt.
 2. A process of claim 1 wherein the reactingstep is carried out in an aprotic medium.
 3. A process of claim 1wherein the reacting step is carried out in a protic medium.
 4. Aprocess of claim 1 wherein the diazonium salt is generated in situ.
 5. Aprocess for preparing a carbon black product having an organic groupattached to the carbon black comprising the step of: reacting at leastone diazonium salt with a carbon black in a protic reaction medium.
 6. Aprocess of claim 5 wherein the diazonium salt is generated in situ froma primary amine.
 7. A process of claim 6 wherein the diazonium salt isgenerated in situ by reacting the primary amine, at least one nitriteand at least one acid.
 8. A process of claim 7 wherein the nitrite is ametal nitrite, and the acid and amine are present in a one to one molarratio.
 9. A process of claim 6 wherein the diazonium salt is generatedin situ by reacting the primary amine with a nitrite and the primaryamine contains a strong acid group.
 10. A process of claim 9 wherein theprimary amine is para-aminobenzenesulfonic acid (sulfanilic acid).
 11. Aprocess of claim 6 wherein the diazonium salt is generated in situ byreacting the primary amine with an aqueous solution of nitrogen dioxide.12. A process of claim 6 wherein the protic medium is an aqueous medium,and the primary amine is an amine of the formula A_(y)ArNH₂, in which:Ar is an aromatic or heteroaromatic radical; A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of R, OR, COR, COOR, OCOR, a carboxylate salt, halogen,CN, NR₂, SO₃H, a sulfonate salt OSO₃H, OSO₃— salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁺, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched or cyclic hydrocarbon radical,unsubstituted or substituted with one or more of said functional groups;where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₂₀ unsubstituted or substituted alkyl,alkenyl, or alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl; orunsubstituted or substituted arylalkyl; wherein k is an integer from 1to 8; X— is a halide or an anion derived from a mineral or organic acid;y is an integer from 1 to the total number of —CH radicals present inthe aromatic radical; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1to 6, and w is 2 to
 6. 13. A process of claim 12 wherein: Ar is anaromatic radical selected from the group consisting of phenyl, naphthyl,anthryl, phenanthryl, biphenyl, and pyridyl; A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of R, OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄⁺, halogen, CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR),CONR₂, NO₂, PO₃H₂, PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, PR₃⁺X⁻, S_(k)R, SOR, and SO₂R; and a linear, branched or cyclic hydrocarbonradical, unsubstituted or substituted with one or more of saidfunctional groups; where R is hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl or alkynyl; unsubstituted orsubstituted aryl; unsubstituted or substituted heteroaryl; unsubstitutedor substituted alkylaryl; or unsubstituted or substituted arylalkyl;wherein k is an integer from 1 to 8; X— is a halide or an anion derivedfrom a mineral or organic acid; and y is an integer from 1 to 5 when Aris phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar is anthryl,phenanthryl, or biphenyl, and 1 to 4 when Ar is pyridyl.
 14. A processof claim 12, wherein: Ar is an aromatic radical selected from the groupconsisting of phenyl, benzothiazolyl, and benzothiadiazolyl; A, whichcan be the same or different when y is greater than 1, is independentlya substituent on the aromatic radical selected from: a functional groupselected from the group consisting of S_(k)R, SSO₃H, SO₂NRR′, SO₂SR,SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),and 2-(1,3-dithiolanyl); and a linear, branched or cyclic hydrocarbonradical, unsubstituted or substituted with one or more of saidfunctional groups; where R and R′, which can be the same or different,are hydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; y is an integerfrom 1-5 when Ar is phenyl, 1-4 when Ar is benzothiazolyl, and 1-3 whenAr is benzothiadiazolyl; k is an integer from 1 to 8; and Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.15. A process of claim 12, wherein R and R′ are selected from NH₂—C₆H₄,CH₂CH₂—C₆H₄—NH₂, CH₂—C₆H₄—NH₂, and C₆H₅.
 16. A process of claim 12,wherein A is (CH₂)_(q)S_(k)(CH₂)_(r)Ar, where k is an integer from 1 to8, q is an integer from 0 to 4, r is an integer from 0-4, and Ar is asubstituted or unsubstituted aryl or heteroaryl group.
 17. A process ofclaim 6 wherein the primary amine is an aminobenzenesulfonic acid or asalt thereof, an aminobenzenecarboxylic acid or a salt thereof, orbis-para-H₂N—(C₆H₄)-S_(k)-(C₆H₄)—NH₂ wherein k is an integer from 2 to8.
 18. A process of claim 17 wherein the primary amine ispara-aminobenzenesulfonic acid (sulfanilic acid).
 19. A process of claim17, wherein the primary amine is bis-para-H₂N—(C₆H₄)-S_(k)-(C₆H₄)—NH₂and k is 2, (para-aminophenyldisulfide).
 20. A process of claim 6wherein the primary amine is H₂NArS_(k)Ar′, where k is an integer from 2to 4, Ar is phenylene, and Ar′ is benzothiazolyl.
 21. A process of claim6 wherein the primary amine is H₂NArS_(k)ArNH₂, where k is an integerfrom 2 to 4 and Ar is benzothiazolylene.
 22. A process of claim 21wherein k is
 2. 23. A process of claim 6 wherein the primary amine isH₂NArSH, where Ar is phenylene or benzothiazolylene.
 24. A process ofclaim 5 wherein the diazonium salt is generated in situ.
 25. A processof claim 5 wherein the diazonium salt is generated from a primary amineseparately from the reacting step.
 26. A process of claim 25 wherein theprotic medium is an aqueous medium, and the primary amine is an amine ofthe formula AyArNH₂, in which: Ar is an aromatic or heteroaromaticradical; A, which can be the same or different when y is greater than 1,is independently a substituent on the aromatic radical selected from: afunctional group selected from the group consisting of R, OR, COR, COOR,OCOR, a carboxylate salt, halogen, CN, NR₂, SO₃H, a sulfonate salt,OSO₃H, OSO₃— salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasicphosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched or cyclichydrocarbon radical, unsubstituted or substituted with one or more ofsaid functional groups; where R and R′, which can be the same ordifferent, are hydrogen; branched or unbranched C₁-C₂₀ unsubstituted orsubstituted alkyl, alkenyl, or alkynyl; unsubstituted or substitutedaryl; unsubstituted or substituted heteroaryl; unsubstituted orsubstituted alkylaryl; or unsubstituted or substituted arylalkyl;wherein k is an integer from 1 to 8; X— is a halide or an anion derivedfrom a mineral or organic acid; y is an integer from 1 to the totalnumber of —CH radicals present in the aromatic radical; and Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.27. A process of claim 25 wherein: Ar is an aromatic radical selectedfrom the group consisting of phenyl, naphthyl, anthryl, phenanthryl,biphenyl, and pyridyl; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofR, OR, COR, COOR, OCOR, COOLi COONa, COOK, COO⁻NR₄ ⁺, halogen, CN, NR₂,SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃H₂,PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, and SO₂R;and a linear, branched or cyclic hydrocarbon radical, unsubstituted orsubstituted with one or more of said functional groups; where R ishydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; wherein k is aninteger from 1 to 8; X— is a halide or an anion derived from a mineralor organic acid; and y is an integer from 1 to 5 when Ar is phenyl, 1 to7 when Ar is naphthyl, 1 to 9 when Ar is anthryl, phenanthryl, orbiphenyl, and 1 to 4 when Ar is pyridyl.
 28. A process of claim 25,wherein: Ar is an aromatic radical selected from the group consisting ofphenyl, benzothiazolyl, and benzothiadiazolyl; A, which can be the sameor different when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ,CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), and2-(1,3-dithiolanyl); and a linear, branched or cyclic hydrocarbonradical, unsubstituted or substituted with one or more of saidfunctional groups; where R and R′, which can be the same or different,are hydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; y is an integerfrom 1-5 when Ar is phenyl, 1-4 when Ar is benzothiazolyl, and 1-3 whenAr is benzothiadiazolyl; k is an integer from 1 to 8; and Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.29. A process of claim 26, wherein R and R′ are selected from NH₂—C₆H₄,CH₂CH₂—C₆H₄—NH₂, CH₂—C₆H₄—NH₂, and C₆H₅.
 30. A process of claim 26,wherein A is (CH₂)_(q)S_(k)(CH₂)_(r)Ar, where k is an integer from 1 to8, q is an integer from 0 to 4, r is an integer from 0-4, and Ar is asubstituted or unsubstituted aryl or heteroaryl group.
 31. A process ofclaim 25 wherein the primary amine is an aminobenzenesulfonic acid or asalt thereof, an aminobenzenecarboxylic acid or a salt thereof, orbis-para-H₂N—(C₆H₄)-S_(k)-(C₆H₄)—NH₂ wherein k is an integer from 2 to8.
 32. A process of claim 31 wherein the primary amine ispara-aminobenzenesulfonic acid (sulfanilic acid).
 33. A process of claim31 wherein the primary amine is bis-para-H₂N—(C₆H₄)-S_(k)-(C₆H₄)—NH₂ andk is 2, (para-aminophenyldisulfide).
 34. A process of claim 25 whereinthe primary amine is H₂NArS_(k)Ar′, where k is an integer from 2 to 4,Ar is phenylene, and Ar′ in benzothiazolyl.
 35. A process of claim 25wherein the primary amine is H₂NArS_(k)ArNH₂, where k is an integer from2 to 4 and Ar is benzothiazolylene.
 36. A process of claim 25 whereinthe primary amine is H₂NArSH, where Ar is phenylene orbenzothiazolylene.
 37. A process of claim 5 wherein the protic reactionmedium is an aqueous medium.
 38. A process of claim 37 wherein theorganic group of the diazonium salt is substituted or unsubstituted andis selected from the group consisting of an aliphatic group, a cyclicorganic group, or an organic compound having an aliphatic portion and acyclic portion.
 39. A process of claim 5 wherein the protic reactionmedium is water.
 40. A process of claim 5 wherein the protic medium isan alcohol-based medium.
 41. A carbon black product prepared accordingto the process of claim
 1. 42. A carbon black product prepared accordingto the process of claim
 5. 43. A carbon black product prepared accordingto the process of claim
 12. 44. A carbon black product preparedaccording to the process of claim
 13. 45. A carbon black productprepared according to the process of claim
 14. 46. A carbon blackproduct of claim 42 wherein the organic group is substituted orunsubstituted and is selected from the group consisting of an aliphaticgroup, a cyclic organic group, or an organic group having an aliphaticportion and a cyclic portion.
 47. A carbon black product of claim 42wherein the organic group is a substituted or unsubstituted aromaticgroup.
 48. A carbon black product of claim 47 wherein an aromatic ringof the aromatic group is an aryl group.
 49. A carbon black product ofclaim 47 wherein an aromatic ring of the aromatic group is a heteroarylgroup.
 50. A carbon black product of claim 47 wherein said aromaticgroup is a group of the formula A_(y)Ar, wherein: Ar is an aromatic orheteroaromatic radical; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofR, OR, COR, COOR, OCOR, a carboxylate salt, halogen, CN, NR₂, SO₃H, asulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, amonobasic or dibasic phosphate salt, PO₃H₂, a monobasic or dibasicphosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′,SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched or cyclic hydrocarbon radical,unsubstituted or substituted with one or more of said functional groups;where R and R′, which can be the same or different, are hydrogen;branched or unbranched C_(—C) ₂₀ unsubstituted or substituted alkyl,alkenyl, or alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene; wherein k is an integer from 1 to 8; X— is a halide or ananion derived from a mineral or organic acid; y is an integer from 1 tothe total number of —CH radicals present in the aromatic radical; and Qis (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.51. A carbon black product of claim 50, wherein said aromatic group is agroup of the formula AyAr, wherein: Ar is an aromatic radical selectedfrom the group consisting of phenyl, naphthyl, anthryl, phenanthryl,biphenyl, and pyridyl; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofR, OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺, halogen, CN, NR₂,SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃H₂,PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, and SO₂R;and a linear, branched or cyclic hydrocarbon radical, unsubstituted orsubstituted with one or more of said functional groups; where R ishydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; unsubstituted or substituted arylalkyl or arylene; wherein kis an integer from 1 to 8; X— is a halide or an anion derived from amineral or organic acid; and y is an integer from 1 to to 5 when Ar isphenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar is anthryl,phenanthryl, or biphenyl, and 1 to 4 when Ar is pyridyl.
 52. A carbonblack product of claim 50, wherein said aromatic group is a group of theformula A_(y)Ar, wherein: Ar is an aromatic radical selected from thegroup consisting of phenyl, naphthyl, benzothiazolyl, andbenzothiadiazolyl; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofS_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), and 2-(1,3-dithiolanyl);and a linear, branched or cyclic hydrocarbon radical, unsubstituted orsubstituted with one or more of said functional groups; where R and R′,which can be the same or different, are hydrogen; branched or unbranchedC₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, alkynyl;unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; unsubstituted orsubstituted arylalkyl, arylene, heteroarylene, or alkylarylene; y is aninteger from 1-5 when Ar is phenyl, 1-7 when Ar is naphthyl, 1-4 when Aris benzothiazolyl, and 1-3 when Ar is benzothiadiazolyl; k is an integerfrom 1 to 8; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1to 6, and w is 2 to
 6. 53. A carbon black product of claim 42 whereinsaid aromatic group is phenyl or naphthyl.
 54. A carbon black product ofclaim 47 wherein said aromatic group is a group of the formula A_(y)Ar,wherein: Ar is an aromatic or heteroaromatic radical; A, which can bethe same or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of OR, COR, COOR, OCOR, a carboxylatesalt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ salts, NR(COR),CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, amonobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻,S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃— salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched or cyclic hydrocarbon radical,unsubstituted or substituted with one or more of said functional groups;where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₂₀ unsubstituted or substituted alkyl,alkenyl, or alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene; wherein k is an integer from 1 to 8; X— is a halide or ananion derived from a mineral or organic acid; y is an integer from 1 tothe total number of —CH radicals present in the aromatic radical; and Qis (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.55. A carbon black product of claim 54, wherein said aromatic group is agroup of the formula A_(y)Ar, wherein: Ar is an aromatic radicalselected from the group consisting of phenyl, naphthyl, anthryl,phenanthryl, biphenyl, and pyridyl; A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻N₄ ⁺,CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂,PO₃H₂, PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, andSO₂R; and a linear, branched or cyclic hydrocarbon radical,unsubstituted or substituted with one or more of said functional groups;where R is hydrogen; branched or unbranched C₁-C₂₀ unsubstituted orsubstituted alkyl, alkenyl, or alkynyl; unsubstituted or substitutedaryl; unsubstituted or substituted heteroaryl; unsubstituted orsubstituted alkylaryl; unsubstituted or substituted arylalkyl orarylene; wherein k is an integer from 1 to 8; X— is a halide or an anionderived from a mineral or organic acid; and y is an integer from 1 to to5 when Ar is phenyl, 1 to 7 when Ar is naphthyl, 1 to 9 when Ar isanthryl, phenanthryl, or biphenyl, and 1 to 4 when Ar is pyridyl.
 56. Acarbon black product of claim 54, wherein said aromatic group is a groupof the formula A_(y)Ar, wherein: Ar is an aromatic radical selected fromthe group consisting of phenyl, benzothiazolyl, and benzothiadiazolyl;A, which can be the same or different when y is greater than 1, isindependently a substituent on the aromatic radical selected from: afunctional group selected from the group consisting of S_(k)R, SSO₃H,SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), and 2-(1,3-dithiolanyl); and a linear, branched orcyclic hydrocarbon radical, unsubstituted or substituted with one ormore of said functional groups; where R and R′, which can be the same ordifferent, are hydrogen; branched or unbranched C₁-C₂₀ unsubstituted orsubstituted alkyl, alkenyl, alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; unsubstituted or substituted arylalkyl, arylene,heteroarylene, or alkylarylene; y is an integer from 1-5 when Ar isphenyl, 1-4 when Ar is benzothiazolyl, and 1-3 when Ar isbenzothiadiazolyl; k is an integer from 1 to 8; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherex is 1 to 6, z is 1 to 6, and w is 2 to
 6. 57. A carbon black productcomprising a carbon black and at least one attached organic group havinga) an aromatic group and b) an acidic group having a pKa of less than11, or a salt of an acidic group having a pKa of less than 11, or amixture of an acidic group having a pKa of less than 11 and a salt of anacidic group having a pKa of less than 11, wherein at least one aromaticgroup of the organic group is directly attached to the carbon black. 58.A carbon black product of claim 57 wherein the acidic group is asulfonic acid group, a sulfinic acid group, a carboxylic acid group, ora phosphonic acid group.
 59. A carbon black product of claim 57 whereinthe acidic group is SSO₃H, OPO₃H₂, or OSO₃H.
 60. A carbon black productof claim 57 wherein the aromatic group is a substituted phenyl group.61. A carbon black product of claim 57 wherein the aromatic group is asubstituted naphthyl group.
 62. A carbon black product of claim 57wherein the organic group is a substituted or unsubstituted sulfophenylgroup or a salt thereof, or the organic group is a substituted orunsubstituted (polysulfo)phenyl group or a salt thereof.
 63. A carbonblack product of claim 57 wherein the organic group is a substituted orunsubstituted carboxyphenyl group or a salt thereof, or the organicgroup is a substituted or unsubstituted (polycarboxy)phenyl group or asalt thereof.
 64. A carbon black product of claim 57 wherein the organicgroup is a substituted or unsubstituted sulfonaphthyl group or a saltthereof, or the organic group is a substituted or unsubstituted(polysulfo)naphthyl group or a salt thereof.
 65. A carbon black productof claim 57 wherein the organic group is a substituted or unsubstitutedcarboxynaphthyl group or a salt thereof, or the organic group is asubstituted or unsubstituted (polycarboxy)naphthyl group or a saltthereof
 66. A carbon black product of claim 57 wherein the organic groupis p-sulfophenyl or a salt thereof.
 67. A carbon black product of claim57 wherein the organic group is p-carboxyphenyl or a salt thereof.
 68. Acarbon black product of claim 57 wherein the organic group is the Nasalt of p-sulfophenyl.
 69. A carbon black product of claim 57 whereinthe organic group is a hydroxysulfophenyl group.
 70. A carbon blackproduct of claim 69 wherein the organic group is4-hydroxy-3-sulfophenyl.
 71. A carbon black product comprising a carbonblack and at least one organic group having a) an aromatic group and b)a cationic group, wherein at least one aromatic group of the organicgroup is attached to the carbon black.
 72. A carbon black product ofclaim 71 wherein the cationic group is a quaternary ammonium group or aquaternary phosphonium group.
 73. A carbon black product of claim 71wherein the aromatic group is a substituted phenyl group.
 74. A carbonblack product of claim 71 wherein the aromatic group is a substitutednaphthyl group.
 75. A carbon black product of claim 71 wherein theorganic group is X⁻R₃N⁺(CH₂)_(y)Ar, wherein Ar is phenylene ornaphthylene; R is independently hydrogen or a C₁-C₂₀ alkyl group; X⁻ isa halide or an anion derived from a mineral or organic acid; and y is aninteger from 0 to
 4. 76. A carbon black product of claim 75, wherein yis
 0. 77. A carbon black product of claim 71, wherein the organic groupis X⁻R₃N⁺CH₂COAr, wherein R is a substituted or unsubstituted C₁-C₁₀alkyl, Ar is phenylene or naphthylene; and X— is a halide or an anionderived from a mineral or organic acid.
 78. A carbon black product ofclaim 71 wherein the organic group is a N-substituted pyridinium group.79. A carbon black product of claim 78, wherein the organic group is—C₅H₄N—R X⁻, where R is a substituted or unsubstituted C₁-C₂₀hydrocarbon, and X— is a halide or an anion derived from a mineral ororganic acid.
 80. A carbon black product comprising a carbon black andat least one attached organic group having a) a C₁-C₁₂ alkyl group andb) an acidic group having a pKa of less than 11, or a salt of an acidicgroup having a pKa of less than 11, or a mixture of an acidic grouphaving a pKa of less than 11 and a salt of an acidic group having a pKaof less than 11, wherein the C₁-C₁₂ alkyl group of the organic group isdirectly attached to the carbon black.
 81. A carbon black product ofclaim 80 wherein the organic group is C₂H₄SO₃H.
 82. A carbon blackproduct comprising a carbon black and at least one organic groupAr(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ attached to the carbon black, wherein Arand Ar′ may be the same or different and are chosen from the groupconsisting of arylene and heteroarylene; k is an integer from 1 to 8; qis an integer from 0 to 4; and r is an integer from 0 to
 4. 83. A carbonblack product of claim 82 wherein Ar and Ar′ are an arylene; k is aninteger from 1 to 8; and q and r are
 0. 84. A carbon black product ofclaim 82 wherein Ar and A′ are phenylene; k is an integer from 2 to 4;and q and r are
 0. 85. A carbon black product of claim 84 wherein k is2.
 86. A carbon black product of claim 82 wherein Ar and Ar′ are aheteroarylene; k is an integer from 1 to 8; and q and r are
 0. 87. Acarbon black product of claim 82 wherein Ar and Ar′ arebenzothiazolylene; k is an integer from 2 to 4; and q and r are
 0. 88. Acarbon black product of claim 87 wherein k is
 2. 89. A carbon blackproduct comprising a carbon black and at least one organic groupAr(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ attached to the carbon black, wherein Ar isan arylene or a heteroarylene; Ar′ is an aryl or a heteroaryl; k is aninteger from 1 to 8; q is an integer from 0 to 4; and r is an integerfrom 0 to
 4. 90. A carbon black product of claim 89 wherein Ar is anarylene; Ar′ is an aryl; k is an integer from 1 to 8; and q and r are 0.91. A carbon black product of claim 89 wherein Ar is phenylene; Ar′ isphenyl; k is an integer from 2 to 4; and q and r are
 0. 92. A carbonblack product of claim 89 wherein Ar is phenylene; Ar′ is a heteroaryl;k is an integer from 1 to 8; and q and r are
 0. 93. A carbon blackproduct of claim 89 wherein Ar is phenylene; Ar′ is benzothiazolyl; k isan integer from 2 to 4; and q and r are
 0. 94. A carbon black productcomprising a carbon black and at least one organic group ArSH attachedto the carbon black, wherein Ar is an arylene or a heteroarylene.
 95. Acarbon black product of claim 94 wherein Ar is phenylene.
 96. A carbonblack product of claim 94 wherein Ar is benzothiazolylene.
 97. A carbonblack product of claim 71, wherein the organic group is Ar—Ar′⁺X⁻,wherein Ar is substituted or unsubstituted phenylene, substituted orunsubstituted naphthylene; Ar′ is substituted or unsubstitutedpyridinium; and X— is a halide or an anion derived from a mineral ororganic acid.
 98. A carbon black product of claim 97, wherein theorganic group is —C₆H₄(NC₅H₅)⁺X⁻.
 99. A process for producing a carbonblack product having an organic group attached to the carbon black,comprising the steps of introducing a carbon black and at least onediazonium salt into a pelletizer; and reacting said diazonium salt withsaid carbon black.
 100. The process of claim 99, wherein the diazoniumsalt is reacted with the carbon black in the presence of water.
 101. Theprocess of claim 99, wherein the diazonium salt is introduced as anaqueous solution or slurry.
 102. The process of claim 99, wherein thecarbon black product is pelletized.
 103. The process of claim 101,wherein the carbon black product is pelletized.
 104. A process forproducing a carbon black product having an organic group attached to thecarbon black, comprising the steps of generating a diazonium salt in thepresence of carbon black in a pelletizer; and reacting said diazoniumsalt with said carbon black.
 105. The process of claim 104, wherein thediazonium salt is generated in the presence of water.
 106. The processof claim 104, wherein the diazonium salt is generated from at least oneprimary amine, at least one acid, and at least one nitrite.
 107. Theprocess of claim 105, wherein the diazonium salt is generated from atleast one primary amine, at least one acid, and at least one nitrite.108. The process of claim 107, wherein the nitrite is introduced intothe pelletizer as an aqueous solution.
 109. The process of claim 107,wherein the amine is introduced into the pelletizer as an aqueoussolution or slurry of an acid salt of the amine.
 110. The process ofclaim 107, wherein the nitrite is introduced into the pelletizer as anaqueous solution and the amine is introduced into the pelletizer as anaqueous solution or slurry of an acid salt of the amine.
 111. Theprocess of claim 107, wherein the amine and the carbon black areintroduced into the pelletizer as a dry mixture.
 112. A plasticcomposition comprising a plastic and a carbon black product preparedaccording to the process of claim
 1. 113. A plastic compositioncomprising a plastic and a carbon black product prepared according tothe process of claim
 5. 114. A paper product comprising paper pulp and acarbon black product having at least one organic group attached to thecarbon black wherein the organic group is substituted with an ionic oran ionizable group.
 115. A paper product of claim 114 wherein the ionicor ionizable group is a sulfonic acid group or a salt thereof, asulfinic acid group or a salt thereof, a carboxylic acid group or a saltthereof, a phosphonic acid group or a salt thereof, or a quaternaryammonium group.
 116. A paper product of claim 114 wherein the organicgroup is a substituted or unsubstituted sulfophenyl group or a saltthereof, or the organic group is a substituted or unsubstituted(polysulfo)phenyl group or a salt thereof.
 117. A paper product of claim114 wherein the organic group is a substituted or unsubstitutedsulfonaphthyl group or a salt thereof, or the organic group is asubstituted or unsubstituted (polysulfo)naphthyl group or a saltthereof.
 118. A paper product of claim 114 wherein the organic group isp-sulfophenyl or a salt thereof.
 119. A rubber composition prepared bythe process comprising mixing rubber and a carbon black productcomprising a carbon black and at least one organic groupAr(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ attached to the carbon black, wherein Arand Ar′, which may be the same or different, are substituted orunsubstituted arylene or heteroarylene groups; k is an integer from 1 to8; q is an integer from 0 to 4; and r is an integer from 0 to
 4. 120. Arubber composition of claim 119 wherein Ar and Ar′ are an arylene; k isan integer from 1 to 8; and q and r are
 0. 121. A rubber composition ofclaim 119 wherein Ar and Ar′ are phenylene; k is an integer from 2 to 4;and q and r are
 0. 122. A rubber composition of claim 121 wherein k is2.
 123. A rubber composition of claim 119 wherein Ar and Ar′ are aheteroarylene; k is an integer from 1 to 8; and q and r are
 0. 124. Arubber composition of claim 119 wherein Ar and Ar′ arebenzothiazolylene; k is an integer from 2 to 4; and q and r are
 0. 125.A rubber composition of claim 124 wherein k is
 2. 126. A rubbercomposition prepared by the process comprising mixing rubber and acarbon black product comprising carbon black and at least one organicgroup Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ attached to the carbon black, whereinAr is an arylene or a heteroarylene; Ar′ is an aryl or a heteroaryl; kis an integer from 1 to 8; q is an integer from 0 to 4; and r is aninteger from 0 to
 4. 127. A rubber composition of claim 126 wherein Aris an arylene; Ar′ is an aryl; k is an integer from 1 to 8; and q and rare
 0. 128. A rubber composition of claim 126 wherein Ar is phenylene;Ar′ is phenyl; k is an integer from 2 to 4; and q and r are
 0. 129. Arubber composition of claim 126 wherein Ar is phenylene; Ar′ is aheteroaryl; k is an integer from 1 to 8; and q and r are
 0. 130. Arubber composition of claim 126 wherein Ar is phenylene; Ar′ isbenzothiazolyl; k is an integer from 2 to 4; and q and r are
 0. 131. Arubber composition prepared by the process comprising mixing rubber anda carbon black product comprising a carbon black and at least oneorganic group ArSH attached to the carbon black, wherein Ar is anarylene or a heteroarylene.
 132. A rubber composition of claim 131wherein Ar is phenylene.
 133. A rubber composition of claim 131 whereinAr is benzothiazolylene.
 134. A rubber composition of claim 119 which iscured.
 135. A rubber composition of claim 126 which is cured.
 136. Arubber composition of claim 131 which is cured.
 137. A rubbercomposition of claim 122 which is cured.
 138. A fiber or textilecomposition comprising a fiber or textile and a carbon black producthaving at least one organic group attached to the carbon black whereinthe organic group is substituted with an ionic or an ionizable group.139. A fiber or textile composition of claim 138 wherein the ionic orionizable group is a sulfonic acid group or a salt thereof, a sulfonicacid group or a salt thereof, a carboxylic acid group or a salt thereof,a phosphonic acid group or a salt thereof, or a quaternary ammoniumgroup.
 140. A fiber or textile composition of claim 138 wherein theorganic group is a substituted or unsubstituted sulfophenyl group or asalt thereof, or the organic group is substituted or unsubstituted(polysulfo)phenyl group or a salt thereof.
 141. A fiber or textilecomposition of claim 138 wherein the organic group is a substituted orunsubstituted sulfonaphthyl group or a salt thereof, or the organicgroup is substituted or unsubstituted (polysulfo)napthyl group or a saltthereof.
 142. A fiber or textile composition of claim 138 wherein theorganic group is p-sulfophenyl or a salt thereof.
 143. A carbon blackproduct comprising a carbon black and at least one organic groupattached to the carbon black, wherein the organic group is an aromaticgroup of the formula A_(y)Ar, wherein: Ar is an aromatic orheteroaromatic radical; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofOR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonatesalt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic ordibasic phosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt,N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, aSSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear,branched or cyclic hydrocarbon radical, unsubstituted or substitutedwith one or more of said functional groups; where R and R′, which can bethe same or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; unsubstituted or substitutedarylalkyl, arylene, heteroarylene, or alkylarylene; wherein k is aninteger from 1 to 8; X⁻ is a halide or an anion derived from a mineralor organic acid; y is an integer from 1 to the total number of —CHradicals present in the aromatic radical; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherex is 1 to 6, z is 1 to 6, and w is 2 to
 6. 144. A carbon black productof claim 143, wherein said aromatic group is a group of the formulaA_(y)Ar, wherein: Ar is an aromatic radical selected from the groupconsisting of phenyl, naphthyl, anthryl, phenanthryl, biphenyl, andpyridyl; A, which can be the same or different when y is greater than 1,is independently a substituent on the aromatic radical selected from: afunctional group selected from the group consisting of OR, COR, COOR,OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺, CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃H₂, PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻,NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, and SO₂R; and a linear, branched orcyclic hydrocarbon radical, unsubstituted or substituted with one ormore of said functional groups; where R is hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; unsubstituted orsubstituted arylalkyl or arylene; wherein k is an integer from 1 to 8;X⁻ is a halide or an anion derived from a mineral or organic acid; and yis an integer from 1 to to 5 when Ar is phenyl, 1 to 7 when Ar isnaphthyl, 1 to 9 when Ar is anthryl, phenanthryl, or biphenyl, and 1 to4 when Ar is pyridyl.
 145. A carbon black product of claim 143, whereinsaid aromatic group is a group of the formula A_(y)Ar, wherein: Ar is anaromatic radical selected from the group consisting of phenyl,benzothiazolyl, and benzothiadiazolyl; A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of S_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ,CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), and2-(1,3-dithiolanyl); and a linear, branched or cyclic hydrocarbonradical, unsubstituted or substituted with one or more of saidfunctional groups; where R and R′, which can be the same or different,are hydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; unsubstituted or substituted arylalkyl, arylene,heteroarylene, or alkylarylene; y is an integer from 1-5 when Ar isphenyl, 1-4 when Ar is benzothiazolyl, and 1-3 when Ar isbenzothiadiazolyl; k is an integer from 1 to 8; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherex is 1 to 6, z is 1 to 6, and w is 2 to
 6. 146. A rubber compositionprepared by the process comprising mixing rubber and a carbon blackproduct having at least one organic group attached to the carbon black,wherein the organic group is A_(y)Ar, wherein: Ar is an aromatic orheteroaromatic radical; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofOR, COR, COOR, OCOR, a carboxylate salt, halogen, CN, NR₂, SO₃H, asulfonate salt, OSO₃H, OSO₃— salts, NR(COR), CONR₂, NO₂, OPO₃H₂, amonobasic or dibasic phosphate salt, PO₃H2, a monobasic or dibasicphosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′,SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched or cyclic hydrocarbon radical,unsubstituted or substituted with one or more of said functional groups;where R and R′, which can be the same or different, are hydrogen;branched or unbranched C₁-C₂₀ unsubstituted or substituted alkyl,alkenyl, or alkynyl; unsubstituted or substituted aryl; unsubstituted orsubstituted heteroaryl; unsubstituted or substituted alkylaryl;unsubstituted or substituted arylalkyl, arylene, heteroarylene, oralkylarylene; wherein k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; y is an integer from 1 tothe total number of —CH radicals present in the aromatic radical; and Qis (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.147. A rubber composition of claim 146, wherein said aromatic group is agroup of the formula A_(y)Ar, wherein: Ar is an aromatic radicalselected from the group consisting of phenyl, benzothiazolyl, andbenzothiadiazolyl; A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofS_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), and 2-(1,3-dithiolanyl);and a linear, branched or cyclic hydrocarbon radical, unsubstituted orsubstituted with one or more of said functional groups; where R and R′,which can be the same or different, are hydrogen; branched or unbranchedC₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, alkynyl;unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; unsubstituted orsubstituted arylalkyl, arylene, heteroarylene, or alkylarylene; y is aninteger from 1-5 when Ar is phenyl, 1-4 when Ar is benzothiazolyl, and1-3 when Ar is benzothiadiazolyl; k is an integer from 1 to 8; and Q is(CH₂)_(w), (CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z), or(CH₂)_(x)S(CH₂)_(z), where x is 1 to 6, z is 1 to 6, and w is 2 to 6.148. A rubber composition of claim 146 which is cured.
 149. A rubbercomposition of claim 147 which is cured.
 150. A carbon black productcomprising a carbon black and at least one organic group ArNH₂ attachedto the carbon black, wherein Ar is a substituted or unsubstitutedarylene.
 151. A carbon black product of claim 150, wherein Ar isphenylene.
 152. A carbon black product comprising a carbon black and atleast one organic group ArQAr′NH₂, wherein Ar and Ar′, which may be thesame or different, are substituted or unsubstituted arylene, and Q isCH₂ or SO₂.
 153. A carbon black product of claim 152, wherein Ar and Ar′are phenylene.
 154. A carbon black product having an organic groupattached to the carbon black, obtainable by a process comprising thestep of reacting at least one diazonium salt with a carbon black in aprotic reaction medium, wherein said diazonium salt is generated in situfrom a primary amine, the protic medium is an aqueous medium, and theprimary amine is an amine of the formula A_(y)ArNH₂, in which: Ar is anaromatic or heteroaromatic radical; y is an integer from 1 to the totalnumber of —CH radicals present in the aromatic radical; and A, which canbe the same or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, branched or unbranched C₃-C₂₀ unsubstituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl; afunctional group selected from the group consisting of OR, COR, COOR,OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphatesalt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ,SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 155. Thecarbon black product of claim 154, wherein Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted alkynyl, unsubstituted or substituted heteroaryl,unsubstituted or substituted alkylaryl, and unsubstituted or substitutedarylalkyl; a functional group selected from the group consisting of OR,COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt,OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasicphosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 156. Thecarbon product of claim 154, wherein Ar is an aromatic or heteroaromaticradical; y is an integer from 1 to the total number of —CH radicalspresent in the aromatic radical; and A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of OR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂,SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z), or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is1 to 6, and w is 2 to 6; and wherein Ar is optionally furthersubstituted with alkyl(s) and/or halogen(s).
 157. The carbon blackproduct of claim 154, wherein Ar is an aromatic or heteroaromaticradical; y is an integer from 1 to the total number of —CH radicalspresent in the aromatic radical; and A, which can be the same ordifferent when y is greater than 1, is a functional group selected fromthe group consisting of a branched or unbranched C₁-C₂₀ substitutedalkyl, branched or unbranched C₃-C₂₀ unsubstituted alkyl, unsubstitutedor substituted alkenyl, unsubstituted or substituted alkynyl,unsubstituted or substituted heteroaryl, unsubstituted or substitutedalkylaryl, and unsubstituted or substituted arylalkyl;
 158. A carbonblack product, having an aromatic group attached to the carbon black,obtainable by a process comprising the step of reacting at least onediazonium salt with a carbon black in a protic reaction medium, whereinsaid aromatic group is a group of the formula A_(y)Ar, in which: Ar isan aromatic or heteroaromatic radical; y is an integer from 1 to thetotal number of CH radicals present in the aromatic radical; and A,which can be the same or different when y is greater than 1, isindependently a substituent on the aromatic radical selected from: afunctional group selected from the group consisting of a branched orunbranched C₁-C₂₀ substituted alkyl, branched or unbranched C₃-C₂₀unsubstituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted alkynyl, unsubstituted or substituted heteroaryl,unsubstituted or substituted alkylaryl, and unsubstituted or substitutedarylalkyl; a functional group selected from the group consisting of OR,COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt,OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasicphosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 159. Thecarbon black product of claim 158, wherein Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, unsubstituted or substituted alkenyl, unsubstitutedor substituted alkynyl, unsubstituted or substituted heteroaryl,unsubstituted or substituted alkylaryl, and unsubstituted or substitutedarylalkyl; a functional group selected from the group consisting of OR,COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonate salt,OSO₃H, SO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic or dibasicphosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt, N═NR, N₂⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear, branched, aromatic, orcyclic hydrocarbon radical, substituted with one or more of saidfunctional groups and/or halogen(s); wherein R and R′, which can be thesame or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 160. Thecarbon black product of claim 158, wherein Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of OR, COR, COOR, OCOR, a carboxylatesalt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR),CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, amonobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻,S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to 6; and wherein Ar is optionally further substitutedwith alkyl(s) and/or halogen(s).
 161. The carbon black product of claim158, wherein Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of-CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is a functional group selected from the group consistingof a branched or unbranched C₁-C₂₀ substituted alkyl, branched orunbranched C₃-C₂₀ unsubstituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted heteroaryl, unsubstituted or substituted alkylaryl, andunsubstituted or substituted arylalkyl;
 162. The carbon black product ofclaim 158, wherein Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of —CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofa branched or unbranched C₁-C₂₀ substituted alkyl, branched orunbranched C₃-C₂₀ unsubstituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted heteroaryl, unsubstituted or substituted alkylaryl, andunsubstituted or substituted arylalkyl; a functional group selected fromthe group consisting of OR, COR, COOR, OCOR, a carboxylate salt, CN,NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups; whereinR and R′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 163. The carbon blackproduct of claim 158, wherein said aromatic group is a group of theformula A_(y)Ar, in which: Ar is an aromatic radical selected from thegroup consisting of phenyl, naphthyl, anthryl, phenanthyl, biphenyl, andpyridyl; y is an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Aris naphthyl, 1 to 9 when Ar is anthryl, phenanthryl, or biphenyl, and 1to 4 when Ar is pyridyl; and A, which can be the same or different wheny is greater than 1, is independently a substituent on the aromaticradical selected from: a functional group selected from the groupconsisting of a branched or unbranched C₁-C₂₀ substituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl; afunctional group selected from the group consisting of OR, COR, COOR,OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺, CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K,SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, X⁻, PR₃⁺X⁻, S_(k)R, SOR, and SO₂R; and a linear, branched, aromatic, or cyclichydrocarbon radical, substituted with one or more of said functionalgroups; wherein R is hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; and X⁻ is a halide or an anionderived from a mineral or organic acid.
 164. The carbon black product ofclaim 158, wherein said aromatic group is a group of the formulaA_(y)Ar, in which: Ar is an aromatic radical selected from the groupconsisting of phenyl, naphthyl, benzothiazolyl, and benzothiadiazolyl; yis an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Ar is naphthyl,1 to 4 when Ar is benzothiazolyl, and 1 to 3 when Ar isbenzothiadiazolyl; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofS_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl); and alinear, branched, aromatic, or cyclic hydrocarbon radical, substitutedwith one or more of said functional groups; wherein R and R′, which canbe the same or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; X⁻ is a halide or an anionderived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 165. The carbon blackproduct of claim 158, wherein Ar is an aromatic or heteroaromaticradical; y is an integer from 1 to the total number of —CH radicalspresent in the aromatic radical; and A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of OR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂,SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups; whereinR and R′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 166. The carbon blackproduct of claim 165, wherein said aromatic group is a group of theformula A_(y)Ar, in which: Ar is an aromatic radical selected from thegroup consisting of phenyl, naphthyl, anthryl, phenanthyl, biphenyl, andpyridyl; y is an integer from 1 to 5 when Ar is phenyl, 1 to 7 when Aris naphthyl, 1 to 9 when Ar is anthryl, phenanthryl, or biphenyl, and 1to 4 when Ar is pyridyl; and A, which can be the same or different wheny is greater than 1, is independently a substituent on the aromaticradical selected from: a functional group selected from the groupconsisting of OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺, CN,NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃—NR₄ ⁺, NR(COR), CONR₂, NO₂, PO₃HNa,PO₃Na₂, N═NR, N₂ ⁺X⁻, X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, and SO₂R; and a linear,branched, aromatic, or cyclic hydrocarbon radical, substituted with oneor more of said functional groups; wherein R is hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; and X⁻ is a halideor an anion derived from a mineral or organic acid.
 167. The carbonblack product of claim 165, wherein said aromatic group is a group ofthe formula A_(y)Ar, in which: Ar is an aromatic radical selected fromthe group consisting of phenyl, benzothiazolyl, and benzothiadiazolyl; yis an integer from 1 to 5 when Ar is phenyl, 1 to 4 when Ar isbenzothiazolyl, and 1 to 3 when Ar is benzothiadiazolyl; and A, whichcan be the same or different when y is greater than 1, is independentlya substituent on the aromatic radical selected from: a functional groupselected from the group consisting of S_(k)R, SSO₃H, SO₂NRR′, SO₂SRSNRR′, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl),2-(1,3-dithiolanyl); and a linear, branched, aromatic, or cyclichydrocarbon radical, substituted with one or more of said functionalgroups; wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)₂, wherein x is 1 to 6, z is 1 to6, and w is 2 to
 6. 168. A carbon black product comprising a carbonblack and at least one organic group attached to the carbon black,wherein the organic group is an aromatic group of the formula A_(y)Ar,wherein: Ar is an aromatic or heteroaromatic radical; y is an integerfrom 1 to the total number of —CH radicals present in the aromaticradical; and A, which can be the same or different when y is greaterthan 1, is independently a substituent on the aromatic radical selectedfrom: a functional group selected from the group consisting of abranched or unbranched C₁-C₂₀ substituted alkyl, branched or unbranchedC₃-C₂₀ unsubstituted alkyl, unsubstituted or substituted akenyl,unsubstituted or substituted alkynyl, unsubstituted or substitutedheteroaryl, unsubstituted or substituted alkylaryl, and unsubstituted orsubstituted arylalkyl; a functional group selected from the groupconsisting of OR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, asulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, amonobasic or dibasic phosphate salt, PO₃H₂, a monobasic or dibasicphosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′,SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to 6; and wherein Ar is optionally further substitutedwith alkyl(s) and/or halogen(s).
 169. The carbon black product of claim168, wherein: Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofa branched or unbranched C₁-C₂₀ substituted alkyl, unsubstituted orsubstituted alkenyl, unsubstituted or substituted alkynyl, unsubstitutedor substituted heteroaryl, unsubstituted or substituted alkylaryl, andunsubstituted or substituted arylalkyl; a functional group selected fromthe group consisting of OR, COR, COOR, OCOR, a carboxylate salt, CN,NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂,OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, a monobasic ordibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R,SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃— salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups and/orhalogen(s); wherein R and R′, which can be the same or different, arehydrogen; branched or unbranched C₁-C₂₀ unsubstituted or substitutedalkyl, alkenyl, or alkynyl; unsubstituted or substituted aryl;unsubstituted or substituted heteroaryl; unsubstituted or substitutedalkylaryl; or unsubstituted or substituted arylalkyl; k is an integerfrom 1 to 8; X⁻ is a halide or an anion derived from a mineral ororganic acid; and Q is (CH₂)_(w), (CH₂)_(x)O(CH₂)_(z),(CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z), wherein x is 1 to 6, z is 1to 6, and w is 2 to 6; and wherein Ar is optionally further substitutedwith alkyl(s) and/or halogen(s).
 170. The carbon black product of claim168, wherein: Ar is an aromatic or heteroaromatic radical; y is aninteger from 1 to the total number of CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofOR, COR, COOR, OCOR, a carboxylate salt, CN, NR₂, SO₃H, a sulfonatesalt, OSO₃H, OSO₃ ⁻ salts, NR(COR), CONR₂, NO₂, OPO₃H₂, a monobasic ordibasic phosphate salt, PO₃H₂, a monobasic or dibasic phosphonate salt,N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, aSSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ, S-(1,4-piperazinediyl)-SR,2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR, and SO₂R; and a linear,branched, aromatic, or cyclic hydrocarbon radical, substituted with oneor more of said functional groups and/or halogen(s); wherein R and R′,which can be the same or different, are hydrogen; branched or unbranchedC₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, or alkynyl;unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to 6; and wherein Ar isoptionally further substituted with alkyl(s) and/or halogen(s).
 171. Thecarbon black product of claim 168, wherein: Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is a functional groupselected from the group consisting of a branched or unbranched C₁-C₂₀substituted alkyl, branched or unbranched C₃-C₂₀ unsubstituted alkyl,unsubstituted or substituted alkenyl, unsubstituted or substitutedalkynyl, unsubstituted or substituted heteroaryl, unsubstituted orsubstituted alkylaryl, and unsubstituted or substituted arylalkyl; 172.The carbon black product of claim 168, wherein: Ar is an aromatic orheteroaromatic radical; y is an integer from 1 to the total number of—CH radicals present in the aromatic radical; and A, which can be thesame or different when y is greater than 1, is independently asubstituent on the aromatic radical selected from: a functional groupselected from the group consisting of OR, COR, COOR, OCOR, a carboxylatesalt, CN, NR₂, SO₃H, a sulfonate salt, OSO₃H, OSO₃ ⁻ salts, NR(COR),CONR₂, NO₂, OPO₃H₂, a monobasic or dibasic phosphate salt, PO₃H₂, amonobasic or dibasic phosphonate salt, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻,S_(k)R, SO₂NRR′, SO₂SR, SNRR′, SSO₃H, a SSO₃ ⁻ salt, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl), SOR,and SO₂R; and a linear, branched, aromatic, or cyclic hydrocarbonradical, substituted with one or more of said functional groups; whereinR and R′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein x is 1 to 6, z is 1 to 6, and w is 2 to
 6. 173. The carbon blackproduct of claim 168, wherein: Ar is an aromatic radical selected fromthe group consisting of phenyl, naphthyl anthryl, phenanthryl, biphenyl,and pyridyl; y is an integer from 1 to the total number of CH radicalspresent in the aromatic radical; and A, which can be the same ordifferent when y is greater than 1, is independently a substituent onthe aromatic radical selected from: a functional group selected from thegroup consisting of OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO⁻NR₄ ⁺,CN, NR₂, SO₃H, SO₃Li, SO₃Na, SO₃K, SO₃ ⁻NR₄ ⁺, NR(COR), CONR₂, NO₂,PO₃H₂, PO₃HNa, PO₃Na₂, N═NR, N₂ ⁺X⁻, NR₃ ⁺X⁻, PR₃ ⁺X⁻, S_(k)R, SOR, andSO₂R; and a linear, branched, aromatic, or cyclic hydrocarbon radical,substituted with one or more of said functional groups; wherein R andR′, which can be the same or different, are hydrogen; branched orunbranched C₁-C₂₀ unsubstituted or substituted alkyl, alkenyl, oralkynyl; unsubstituted or substituted aryl; unsubstituted or substitutedheteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted orsubstituted arylalkyl; k is an integer from 1 to 8; X⁻ is a halide or ananion derived from a mineral or organic acid.
 174. The carbon blackproduct of claim 168, wherein: Ar is an aromatic radical selected fromthe group consisting of phenyl, benzothiazolyl, and benzothiadiazolyl; yis an integer from 1 to the total number of —CH radicals present in thearomatic radical; and A, which can be the same or different when y isgreater than 1, is independently a substituent on the aromatic radicalselected from: a functional group selected from the group consisting ofS_(k)R, SSO₃H, SO₂NRR′, SO₂SR, SNRR′, SNQ, SO₂NQ, CO₂NQ,S-(1,4-piperazinediyl)-SR, 2-(1,3-dithianyl), 2-(1,3-dithiolanyl); and alinear, branched, aromatic, or cyclic hydrocarbon radical, substitutedwith one or more of said functional groups; wherein R and R′, which canbe the same or different, are hydrogen; branched or unbranched C₁-C₂₀unsubstituted or substituted alkyl, alkenyl, or alkynyl; unsubstitutedor substituted aryl; unsubstituted or substituted heteroaryl;unsubstituted or substituted alkylaryl; or unsubstituted or substitutedarylalkyl; k is an integer from 1 to 8; and Q is (CH₂)_(w),(CH₂)_(x)O(CH₂)_(z), (CH₂)_(x)NR(CH₂)_(z) or (CH₂)_(x)S(CH₂)_(z),wherein X is 1 to 6, z is 1 to 6, and w is 2 to
 6. 175. A carbon blackproduct comprising a carbon black and at least one organic group havinga) an aromatic group and b) a cationic group, wherein at least onearomatic group of the organic group is attached to the carbon black andwherein the organic group is a N-substituted pyridinium group.
 176. Acarbon black product comprising a carbon black and at least one organicgroup ArOH attached to the carbon black, wherein Ar is arylene orheteroarylene.
 177. A carbon black product comprising a carbon black andat least one organic group Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′ attached to thecarbon black, wherein Ar and Ar′ are arylene, k is an integer from 1 to8, and q and r are
 0. 178. A carbon black product comprising a carbonblack and at least one organic group Ar(CH₂)_(q)S_(k)(CH₂)_(r)Ar′attached to the carbon black, wherein Ar and Ar′ are heteroarylene, k isan integer from 1 to 8, and q and r are
 0. 179. A process for preparinga carbon black product having an organic group attached to the carbonblack comprising the step of: reacting at least one diazonium salt witha carbon black in a protic reaction medium, wherein the diazonium saltis generated in situ from the primary amine H₂NArS_(k)ArNH₂ wherein Aris benzothiazolylene and k is
 2. 180. A plastic composition comprising aplastic and the carbon product according to claim
 154. 181. A paperproduct comprising paper pulp and the carbon product according to claim154.
 182. A fiber or textile composition comprising a fiber or textileand the carbon black product according to claim
 154. 183. An elastomercomposition obtainable by mixing at least one elastomer and the carbonblack product according to claim
 154. 184. The elastomer composition ofclaim 183, wherein the elastomer comprises at least one synthetic ornatural polymer of 1,3-butadiene, styrene, isoprene, isobutylene,2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene, or propylene. 185.The elastomer composition of claim 184, further comprising at least oneadditive selected from the group consisting of: a curing agent, acoupling agent, a processing aid, an oil extender, and an antioxidant.186. A cured elastomer composition obtainable by curing the elastomercomposition of claim
 183. 187. A rubber composition obtainable by mixinga rubber and the carbon black product according to claim
 154. 188. Therubber composition of claim 187, wherein the rubber comprises a naturalrubber, a synthetic rubber, or mixtures or a natural and syntheticrubber.
 189. The rubber composition of claim 188, wherein the rubber isselected from the group consisting of: copolymers of from about 10 toabout 70 percent by weight of styrene and from about 90 to about 30percent by weight of butadiene, polymers of conjugated dienes, andcopolymers of conjugated dienes with ethylenic group-containingmonomers.
 190. The rubber composition of claim 189, wherein the rubberis a rubber selected from the group consisting of: polybutadiene,polyisoprene, polychloroprene, and poly(styrene-butadiene).
 191. Therubber composition of claim 190, further comprising at least oneadditive selected from the group consisting of: a curing agent, acoupling agent, a processing aid, an oil extender, and an antioxidant.192. A cured rubber composition obtainable by curing the rubbercomposition of claim
 187. 193. A tire or tire component comprising theelastomer composition of claims
 183. 194. A tire or tire componentcomprising the rubber composition of claims
 187. 195. A method ofdecreasing the tan delta max at 70 deg C. of an elastomer compositioncomprising the step of combining an elastomer with at least one carbonblack product of claims
 154. 196. The method of claim 195, furthercomprising forming the elastomer composition into a tire or tirecomponent.
 197. A method of increasing the abrasion resistance of anelastomer composition comprising the step of combining an elastomer withat least one carbon black product of claim
 154. 198. The method of claim197, further comprising forming the elastomer composition into a tire ortire component.